Positive photoresist formulation using a crosslinkable siloxane compound

Abstract

The present invention relates to a positive photoresist formulation comprising a crosslinkable siloxane polymer. The siloxane polymer used in the positive photoresist formulation is crosslinkable and comprises a first repeating unit containing at least one maleimide group and a second repeating unit not containing a maleimide group. The present invention further provides a method for manufacturing a microelectronic structure using the positive photoresist formulation according to the present invention and an electronic device comprising the microelectronic structure, which is obtained or obtainable by the manufacturing method.

Description

Field of the Invention

[0001] The present invention relates to a positive photoresist formulation comprising a crosslinkable siloxane polymer. The siloxane polymer used in the positive photoresist formulation is crosslinkable and comprises a first repeating unit containing at least one maleimide group and a second repeating unit free of maleimide groups.

[0002] The positive photoresist formulation is photopatternable and is particularly suitable for preparing dielectric materials having excellent barrier, passivation and / or planarization properties. The photoresist formulation can be used in various applications in the electronics industry, where, in the case of insulation, protective or barrier materials in the form of layers, films or coatings are required, such as, for example, in electronic packaging or in the preparation of field effect transistors (FETs) or thin film transistors (TFTs) of electronic devices. The dielectric material can form a barrier coating, a passivation layer, a planarization layer or a combined passivation and planarization layer on a conductor or semiconductor structure (such as, for example, in an FET or a TFT). In addition, the material can be used to prepare substrates for printed circuit boards. The photoresist formulation can be cured under thermal conditions at low temperatures or by applying only UV radiation.

[0003] The cured dielectric material obtained from the positive photoresist formulation exhibits excellent film-forming ability, excellent thermal properties, excellent mechanical properties and is easily handled and processed by conventional solvents. In addition, the obtained material is characterized by a low dielectric constant and a low coefficient of thermal expansion (CTE). Due to the favorable and well-balanced relationship between the hardness and elasticity of the material, the thermal stress that can be generated during the operation of an electronic device can be easily compensated.

[0004] The present invention further provides a method of manufacturing a microelectronic structure using the positive photoresist formulation according to the present invention and an electronic device comprising the microelectronic structure, which microelectronic structure is obtained or obtainable by the manufacturing method. Background of the Invention

[0006] To date, various materials have been described for preparing dielectric materials in the electronics industry. For example, US 2012 / 0056249 A1 relates to polycyclic olefins based on norbornene-type polymers and their use for preparing dielectric interlayers of fluoropolymer layers applied to electronic devices.

[0007] WO 2017 / 144148 A1 provides a positive photosensitive siloxane composition capable of forming a cured film, such as a planarization film or an interlayer insulating film for a TFT substrate. The positive photosensitive siloxane composition comprises (I) a polysiloxane having a substituted or unsubstituted phenyl group, (II) a diazonaphthoquinone derivative, (III) a hydrate or solvate of a photo-base generator, and (IV) a solvent.

[0008] US 2013 / 0099228 A1 relates to a passivation layer solution composition containing an organosiloxane resin represented by the following formula:

[0009]

[0010] wherein R is at least one substituent selected from a saturated hydrocarbon or an unsaturated hydrocarbon having 1 to about 25 carbon atoms, and x and y may each independently be 1 to about 200, and wherein each asterisk indicates a bond to an H atom, or to x siloxane units or y siloxane units, or to x siloxane units or y siloxane units of another siloxane chain comprising x siloxane units or y siloxane units, or a combination thereof. The passivation layer solution composition is used to prepare a passivation layer on an oxide semiconductor in a thin film transistor (TFT) array panel.

[0011] The passivation layer in the oxide semiconductor should be a passivation layer that inhibits moisture, hydrogen, and oxygen. The penetration of these impurities significantly changes the conductivity of the oxide semiconductor and inhibits operational stability, causing threshold fluctuations. Passivation layers suitable for TFT applications (such as SiO x 、SiON x 、SiN x The main methods of producing oxide semiconductors are chemical vapor deposition (CVD) or physical vapor deposition (PVD). These vapor deposition techniques have the problem of being harmful to the oxide semiconductor layer. In addition, in the production of oxide semiconductor devices, there is a concern that the oxide semiconductor may be further deteriorated by various chemicals or by processes such as dry etching. Therefore, as a protection against this process, a protective film such as an etching plug may be applied. Therefore, in order to overcome these shortcomings, it has been proposed to apply a liquid protective film to the substrate by a wet coating method (JP 2015 / 146332 A).

[0012] Furthermore, US 2007 / 0205399 A1 relates to functionalized cyclic siloxanes useful as thermosetting adhesive resins for the electronic packaging industry, and US 2011 / 0319582 A1 relates to curable compositions comprising a reaction product obtained by reacting an alkoxysilane compound with inorganic oxide microparticles in the presence of water and an organic solvent.

[0013] As is apparent from the above, organopolysiloxanes are a very interesting class of compounds due to their thermal stability and mechanical hardness and their use in a variety of different applications, such as, for example, for forming cured films having high heat resistance, transparency and resolution. Organopolysiloxanes having methyl and / or phenyl side groups are used as dielectric materials in the electronics industry (mainly in the front-end of line (FEOL)), where heat-stable materials are required. These materials have a tolerance temperature of up to 600 °C. However, known materials are too rigid and brittle for use in back-end of line (BEOL) applications (i.e., as redistribution, stress buffer or passivation layers), where the temperature requirements are slightly lower (250 to 300 °C), but the mechanical properties become much more important, such as elongation and thermal expansion.

[0014] Flexible material systems are needed to prevent device cracking or coating delamination. Typically, to tune the desired mechanical, thermal and / or electrical properties, these material systems are modified and adapted to specific application requirements through the concept of compound blending of currently more than ten different compounds. Advantageously, organopolysiloxane-based polymers can be customized to overcome possible drawbacks, such as poor adhesion, poor elongation or high thermal expansion / contraction and can prevent compound multi-component solutions.

[0015] Accordingly, there is a continuing need to develop novel compounds that can be used as dielectric materials or barrier coating materials for various applications in the electronics industry, such as, for example, for the encapsulation of microelectronic devices or for the preparation of field effect transistors (FETs) or thin film transistors (TFTs).

[0016] Object of the invention

[0017] The present invention has been achieved in view of the above background and aims to provide a positive photosensitive resist formulation that does not emit harmful volatile substances (such as, for example, benzene), and that can form a pattern of a dielectric material having high resolution, high heat resistance, low dielectric constant, good adhesion to multiple surfaces, high flexibility and a low coefficient of thermal expansion that prevents the substrate from bending and delaminating during heating and cooling.

[0018] In the manufacturing process of a photo-patterned passivation layer, the deposited layer of the dielectric material precursor must undergo different process steps, such as Figure 1 as shown. The problem that arises here is that multiple additives must be used to obtain a formulation that permits sufficient and satisfactory patterning. The formulation needs to meet specific criteria, such as being applicable by spin coating, suitable for forming a uniform coating on a wafer, showing photosensitivity to UV light, being developable with an aqueous solution (such as TMAH / H2O) and allowing the formation of a stable pattern at temperatures up to 230 °C without cracking.

[0019] It has been found that standard silicone coatings do not meet the above criteria. Therefore, additives need to be incorporated into the photoresist composition to enhance its performance or even make it function as desired. In addition, standard silicone photoresist formulations have been shown to flow rapidly upon heating during the post-baking step, resulting in poor or even no patterning on the substrate. Therefore, additives such as photoacid generators (PAGs) are added to overcome this defect. Some materials obtained from photoresist formulations known in the prior art are extremely brittle and thus have a very low cracking threshold, making it difficult to cast a uniform film with a thickness greater than about 2 μm that is resistant to temperatures above 200 °C.

[0020] Another problem is the solubility of the additives in common solvents and polysiloxanes. Some additives such as, for example, PAGs or photoactive compounds need to be completely dissolved to prevent non-uniformities or particle formation in the film. All these problems should be minimized to achieve the proper performance of the electronic device. Currently, known photoresist formulations consist of up to 20 different components to meet all requirements. However, this complex mixture can adversely affect the performance of the electronic device such that further optimization of a good performance formulation is extremely challenging. The use of additives additionally increases the cost of the formulation and complicates reproducibility.

[0021] Accordingly, an object of the present invention is to overcome the drawbacks in the prior art and to provide a novel positive photoresist formulation that allows the preparation of dielectric materials having excellent barrier, passivation, and / or planarization properties, which can be used in various applications in the electronics industry. Preferred applications are, for example, electronic packaging or the fabrication of FET or TFT devices. The dielectric material can be used to structure redistribution layers (RDLs) in encapsulated microelectronic devices or to form barrier coatings, passivation layers, planarization layers, or combined passivation and planarization layers on conductor or semiconductor structures.

[0022] In addition, an object of the present invention is to provide a novel positive photoresist formulation for the preparation of dielectric materials that, when used to form a passivation layer in an encapsulated electronic device, exhibits excellent film-forming ability, excellent photosensitivity and photopatternability, excellent thermal properties such as, for example, a low coefficient of thermal expansion, and excellent mechanical properties such as, for example, excellent flexibility and adhesion. Another object is to provide a novel photoresist formulation that can be produced at low cost and that allows easy handling and processing with conventional solvents.

[0023] In addition to this, an object of the present invention is to provide a method for manufacturing a microelectronic structure using the positive photoresist formulation and to provide an electronic device comprising the microelectronic structure. Summary of the Invention

[0025] The inventors have surprisingly found that the above objects are achieved by a positive photoresist formulation comprising:

[0026] (a) A silicone polymer comprising a first repeating unit and a second repeating unit; and

[0027] (b) A photoactive dissolution regulator;

[0028] wherein the first repeating unit contains at least one maleimide group; and the second repeating unit does not contain a maleimide group.

[0029] The positive photoresist formulation according to the present invention exhibits excellent performance, even without the addition of a photoacid generator (PAG), and allows for the cost-effective and reliable manufacture of microelectronic devices.

[0030] Furthermore, a method for manufacturing a microelectronic structure is provided, which comprises the following steps:

[0031] (1) Applying the positive photoresist formulation according to the present invention to the surface of a substrate;

[0032] (2) Photopatterning the positive photoresist formulation applied in step (1) to obtain a photopatterned structure; and

[0033] (3) Curing the photopatterned structure obtained in step (2) to obtain a cured photopatterned dielectric material on the surface of the substrate.

[0034] Finally, an electronic device is provided, which comprises a microelectronic structure obtainable or obtained by the manufacturing method according to the present invention.

[0035] The preferred embodiments of the present invention are described below and in the independent claims. Brief Description of the Drawings

[0037] Figure 1 : A manufacturing method for preparing a photopatterned passivation layer. Step (I): A polysiloxane coating, spin-coated / slit-coated, pre-baked at 100 °C for 90 seconds; Step (II): Exposure, photopatterning, UV light (g, h, i-lines), 50 to 300 mJ / cm 2 ; Step (III) Development, 2.38% TMAH / water, rinsed with deionized water; Step (IV) Whole-wafer exposure, UV light (g, h, i-lines), 200 to 600 mJ / cm 2 , for bleaching; and Step (V) Post-baking, heated at 230 °C for 90 minutes.

[0038] Figure 2a : Photopatterning of the photoresist formulation of reference 100. Left: After development. Right: After post-baking.

[0039] Figure 2b : Photopatterning of the photoresist formulation of Example 101. Left: After development. Right: After post-baking.

[0040] Detailed Description

[0041] Electronic Packaging

[0042] As solid state transistors began to replace vacuum tube technology, electronic components (such as resistors, capacitors, and diodes) were to be mounted directly to the printed circuit board of the card through their leads, making it possible to establish the basic building blocks or packaging levels still in use today. Complex electronic functions often require more individual components that can be interconnected on a single printed circuit card. Multilayer card capability was accompanied by the development of three-dimensional packaging of daughter cards to multilayer mother cards. Integrated circuits allowed many discrete circuit components (such as resistors and diodes) to be embedded in individual relatively small components called integrated circuit chips or dies. Despite the incredible circuit integration, however, more than one packaging level is often required, partly due to the integrated circuit technology itself. Integrated circuit chips are very fragile and have extremely small terminals. The primary function of the first-level packaging is to achieve the main functions of mechanical protection, cooling, and the ability to provide electrical connections to the delicate integrated circuits. At least one additional packaging level, such as a printed circuit card, is utilized because some components (high-power resistors, mechanical switches, capacitors) are not easily integrated onto the chip. For very complex applications, such as mainframe computers, a hierarchy of multiple packaging levels is required.

[0043] As a result of Moore's Law, advanced electronic packaging strategies are playing an increasingly important role in the development of more powerful electronic products. In other words, as the demand for smaller, faster, and more functional mobile and portable electronic devices increases, the demand for improved cost-effective packaging technologies is also increasing. A wide variety of advanced packaging technologies exist to meet the requirements of today's semiconductor industry. The dominant advanced packaging technologies (wafer-level packaging (WLP), fan-out wafer-level packaging (FOWLP), 2.5D interposer, chip-on-chip stacking, package-on-package stacking, embedded IC) all require the structuring of thin substrates, redistribution layers, and other components such as high-resolution interconnects. The end consumer market presents an ongoing push for lower prices and higher functionality on even smaller and thinner devices. This drives the demand for next-generation packaging with finer features and improved reliability at competitive manufacturing costs.

[0044] Wafer-level packaging (WLP) is a technology for packaging integrated circuits while still being part of the wafer, different from more conventional chip-level packaging methods where the wafer is cut into individual circuits (die) and then packaged. WLP offers several major advantages compared to chip-level packaging technologies and is essentially a true chip-scale packaging (CSP) technology since the resulting package is actually the same size as the die. Wafer-level packaging allows the integration of wafer fabrication, packaging, testing, and burn-in at the wafer level to improve the efficiency of the manufacturing process that the device experiences from silicon start to consumer shipment. The main application areas of WLP are smartphones and wearables due to their size constraints. The functions provided by WLP in smartphones or wearables include: compass, sensors, power management, wireless, etc. Wafer-level chip-scale packaging (WL-CSP) is one of the smallest packages available on the market currently. WLP can be classified into fan-in and fan-out type WLP. Both of them use redistribution technology to form connections between the chip and the solder balls.

[0045] Fan-out wafer-level packaging (FOWLP) is one of the most recent packaging trends in microelectronics: FOWLP has high miniaturization potential in both packaging volume and packaging thickness. The technical basis of FOWLP is a reconfigured coated wafer with embedded chips and a thin-film redistribution layer, which together form a surface-mount device (SMD)-compatible package. The main advantages of FOWLP are extremely thin (due to substrate-less packaging), low thermal resistance, and good high-frequency properties, due to short and planar electrical connections together with bump-less chip connections instead of, for example, wire bonding or solder contacts.

[0046] Using current materials, the WLP process is limited to medium chip-size applications. The reason for this limitation is mainly due to the current material selection, which shows a thermal mismatch with the silicon die and can thus reduce performance and generate stress on the die. Novel materials with better mechanical properties (especially, a coefficient of thermal expansion (CTE) close to that of silicon) are highly demanded. Currently, the redistribution layer (RDL) is made of a copper layer that is electroplated on a polymer passivation layer such as polyimide (PI), benzocyclobutene (BCB), or polybenzoxazole (PBO). In addition to photo-patternability, low curing temperature is two other important requirements for these materials.

[0047] Thin-film transistor (TFT)

[0048] Thin film transistor (TFT) array panels are commonly used as circuit boards to independently drive pixels in liquid crystal, electrophoretic particle / liquid, organic electroluminescent (EL) display devices, quantum dot electroluminescence, and light-emitting diodes. The TFT array panel includes scan lines or gate lines that transmit scan signals, image signal lines or data lines that transmit image signals, thin film transistors connected to the gate lines and data lines, and pixel electrodes connected to the thin film transistors. The TFT includes a gate electrode that is part of the gate line, a semiconductor layer that forms a channel, a source electrode that is part of the data line, and a drain electrode. For oxide-based TFTs, the oxide semiconductor layer can be composed of indium oxide, zinc oxide, and gallium oxide, but it can also be composed of some other oxides as long as it exhibits semiconductor characteristics. The TFT is a switching component that controls the switching of image signals transmitted to the pixel electrodes through the data lines according to the scan signals transmitted through the gate lines.

[0049] For the deposition of silicon nitride / silicon oxide layers on silicon or oxide semiconductor substrates, two methods are currently used:

[0050] ● Low-pressure chemical vapor deposition (LPCVD) technology, which operates at a relatively high temperature and is carried out in a vertical or horizontal tube furnace; or

[0051] ● Plasma-enhanced chemical vapor deposition (PECVD) technology, which operates at a relatively low temperature and under vacuum conditions.

[0052] Empirically, SiNx films with a thickness of 200 nm and greater prepared by LPCVD tend to crack easily under changes in pressure or temperature. The process temperature is too high to be applied to glass substrates and hydrogenated amorphous silicon or oxide semiconductors. SiNx films prepared by PECVD have less tensile stress, but they still cause curling of the glass substrate as the size of the glass substrate increases. It also has poor electrical properties. The plasma can also damage thin film semiconductors, especially oxide semiconductors, to reduce TFT performance.

[0053] The photo-structuring of the SiN layer requires many steps, including photoresist coating, photolithography patterning, SiN x etching, photoresist stripping, cleaning, etc. These procedures are time-consuming and costly. Therefore, a novel type of material is needed to passivate the semiconductor layer in the TFT, which forms part of the TFT array panel.

[0054] Definition

[0055] The term "polymer" includes, but is not limited to, homopolymers, copolymers (e.g., block copolymers, random copolymers, and alternating copolymers), terpolymers, quaterpolymers, etc., and blends and variants thereof. In addition, unless otherwise explicitly restricted, the term "polymer" shall include all possible configurational isomers of the material. These configurations include, but are not limited to, isotactic, syndiotactic, and atactic symmetries. A polymer is a molecule of relatively high molecular weight that essentially comprises a multiplicity of repeats (i.e., repeating units) of units derived, in fact or conceptually, from molecules of low relative mass (i.e., monomers). In the context of the present invention, the term "polymer" shall also include dimers, trimers, tetramers, and oligomers of one or more polymers.

[0056] Preferably, in the context of the present invention, a polymer comprises at least 2, more preferably at least 5, even more preferably at least 10, still more preferably at least 30, and most preferably at least 60 monomers.

[0057] As used herein, the term "monomer" refers to a polymerizable compound that can undergo polymerization to contribute a structural unit (repeating unit) to the basic structure of a polymer or oligomer. A polymerizable compound is a functionalized compound having one or more polymerizable groups. A large number of monomers combine in a polymerization reaction to form a polymer. A monomer having one polymerizable group is also referred to as a "monofunctional" or "monoreactive" compound, a compound having two polymerizable groups is referred to as a "bifunctional" or "di-reactive" compound, and a compound having more than two polymerizable groups is referred to as a "polyfunctional" or "polyreactive" compound. A compound having no polymerizable groups is also referred to as a "non-functional" or "non-reactive" compound.

[0058] As used herein, the term "homopolymer" represents a polymer derived from one (real, implied, or hypothetical) monomer.

[0059] As used herein, the term "copolymer" generally means any polymer derived from more than one monomer, wherein the polymer contains more than one corresponding repeating unit. In one embodiment, the copolymer is the reaction product of two or more monomers and thus contains two or more corresponding repeating units. Preferably, the copolymer contains two, three, four, five, or six repeating units. A copolymer obtained by copolymerization of three monomer species may also be referred to as a terpolymer. A copolymer obtained by copolymerization of four monomer species may also be referred to as a quaterpolymer. Copolymers can be presented as block copolymers, random copolymers, and / or alternating copolymers.

[0060] As used herein, the term "block copolymer" represents a copolymer in which adjacent blocks are compositionally distinct, i.e., adjacent blocks contain repeating units derived from different monomer species or derived from the same monomer species but having different compositions or sequence distributions of repeating units.

[0061] In addition, as used herein, the term "random copolymer" refers to a polymer formed from macromolecules in which the probability of finding a given repeating unit at any given site in the chain is independent of the nature of the adjacent repeating units. Typically, in a random copolymer, the sequence distribution of the repeating units follows Bernoullian statistics.

[0062] As used herein, the term "alternating copolymer" represents a copolymer composed of macromolecules that contain two repeating units in an alternating sequence.

[0063] "Siloxane" is a chemical compound having the general formula R3Si[OSiR2] n OSiR3 or (RSi) n O 3n / 2 wherein R can be a hydrogen atom or an organic group and n is an integer ≥ 1. Compared with silanes, the silicon atoms of siloxanes are not directly connected to each other, but are connected via an intermediate oxygen atom: Si-O-Si. Depending on the chain length, siloxanes can occur as straight-chain or branched or cubic or ladder-type or random oligomers or polymeric siloxanes (i.e., oligomeric siloxanes or polysiloxanes). In the case where at least one substituent R is an organic group, the siloxane is called an organosiloxane.

[0064] As used herein, "halogen" refers to the elements belonging to Group 17 of the periodic table. Group 17 of the periodic table contains the chemically related elements fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and astatine (At).

[0065] As explained above, "electronic packaging" is a major discipline within the field of electronic engineering and encompasses a wide variety of technologies. It refers to inserting discrete components, integrated circuits, and MSI (medium-scale integration) and LSI (large-scale integration) chips (usually connected to a lead frame by beam leads) through holes in a multi-layer circuit board (also called a card), and soldering them in place on the multi-layer circuit board. The packaging of an electronic system must consider protection against mechanical damage, cooling, radio frequency noise emission, protection against electrostatic discharge maintenance, operator convenience, and cost.

[0066] As used herein, the term "microelectronic device" refers to an electronic device with extremely small electronic designs and components. Usually but not always, this means micron-scale or smaller. These devices typically contain one or more microelectronic components, which are fabricated from semiconductor materials and interconnected in a packaging structure to form a microelectronic device. Many of the electronic components of normal electronic designs are available in microelectronic equivalents. These include transistors, capacitors, sensors, resistors, diodes, and natural insulators and conductors are all visible in microelectronic devices. Unique wiring techniques (such as wire bonding) are also commonly used in microelectronics because of the extremely small size of the components, leads, and pads.

[0067] As used herein, the term "field effect transistor" or "FET" refers to a transistor that uses an electric field to control the electrical behavior of a device. An FET is also referred to as a unipolar transistor because it involves single-carrier type operation. Many different embodiments of field effect transistors exist. Field effect transistors generally exhibit extremely high input impedance at low frequencies. The conductivity between the drain terminal and the source terminal is controlled by an electric field in the device, which is generated by a voltage difference between the body of the device and the gate.

[0068] As used herein, the term "thin film transistor" or "TFT" refers to a specific type of transistor fabricated by depositing thin films of an active semiconductor layer, a dielectric layer, and metal contacts on a supporting (but non-conductive) substrate. A common substrate is glass because the primary application of TFTs is in liquid crystal displays (LCDs). This is different from conventional transistors where the semiconductor material is typically the substrate, such as a silicon wafer. TFTs can be used to form TFT array panels for use in liquid crystal display (LCD) devices.

[0069] As used herein, the term "photoresist" refers to a photosensitive material used in several processes such as photolithography and photogravure to form a patterned coating on a surface. This process is crucial in the electronics industry. The process begins by coating a substrate with the photosensitive material. Then a patterned mask is applied to the surface to block light such that only the unmasked areas of the material are exposed to light. Then a solvent (referred to as a developer) is applied to the surface. In the case of a positive photoresist, the photosensitive material reacts with light to become more soluble than the unexposed portions and the developer dissolves the areas exposed to light, leaving a coating where the mask was placed. In the case of a negative photoresist, the photosensitive material is strengthened (polymerized or crosslinked) by light, and the developer only dissolves the areas not exposed to light, leaving a coating in the areas where the mask was not placed.

[0070] As used herein, the terms "photoacid" and "photoacid generator" (PAG) refer to molecules that become more acidic upon light absorption. This is due to the formation of a strong acid upon photo-dissociation or the dissociation of a proton upon photo-association (e.g., ring closure). There are two main types of molecules that release a proton upon irradiation: photoacid generators (PAGs) and photoacids (PAHs). PAGs irreversibly undergo proton photo-dissociation, while PAHs are molecules that undergo proton photo-dissociation and thermal re-association. In this case, the excited state is strongly acidic but reversible. An example of photo-dissociation is the triphenylsulfonium trifluoromethanesulfonate having the formula [(C6H5)3S][CF3SO3]. This colorless salt consists of a sulfonium cation and a trifluoromethanesulfonate anion. Many related salts are known, including those having other non-coordinating anions and those having different substituents on the benzene ring. The triphenylsulfonium salt absorbs at 233 nm, which induces the series of reactions shown below. Since this series of reactions is irreversible, triphenylsulfonium trifluoromethanesulfonate is a photoacid generator (PAG).

[0071] [(C6H5)3S][CF3SO3] + hν → [(C6H5)2S][CF3SO3] + C6H5 .

[0072] [(C6H5)2S . [CF3SO3] + C6H5 . → (C6H5C6H4)(C6H5)S + [CF3SO3]H

[0073] As used herein, the term "photoactive dissolution regulator" refers to a compound that converts a photoresist into a derivative soluble in a suitable developer upon exposure to light. During masking and patterning of the photoresist, part of the photoresist film is exposed to light while others remain unexposed. In the unexposed areas of a positive photoresist film, the photoresist remains insoluble in the developer, while in the exposed areas, the photoactive dissolution regulator forms a soluble substance that makes the photoresist soluble in the developer.

[0074] Preferred Embodiment

[0075] Positive Photoresist Formulation

[0076] In a first aspect, the present invention relates to a positive photoresist formulation comprising:

[0077] (a) a silicone polymer comprising a first repeating unit and a second repeating unit; and

[0078] (b) a photoactive dissolution regulator;

[0079] wherein the first repeating unit contains at least one maleimide group; and the second repeating unit does not contain a maleimide group.

[0080] The maleimide group is a functional group represented by the following structure:

[0081]

[0082] wherein R 1 and R 2 are the same as or different from each other and each independently represents H or a substituent. If R 1 and R 2 are both H, the maleimide group is an unsubstituted maleimide group. If at least one of R 1 and R 2 is a substituent different from H, the maleimide group is a substituted maleimide group. represents the connection point of the maleimide group to the remaining structure of the first repeating unit.

[0083] The synthesis of the maleimide-functionalized trialkoxysilane is described in CN 104447849 A.

[0084] Siloxane polymer

[0085] The synthesis of the siloxane polymer is described in PCT / EP2020 / 055952, which claims the priority of EP application No. 19161650.7.

[0086] First repeating unit

[0087] In a preferred embodiment, the first repeating unit is derived from a first siloxane monomer represented by the following formula (1):

[0088]

[0089] wherein:

[0090] L 1 , L 2 and L 3 are the same as or different from each other and each independently selected from R, OR and halogen, wherein at least one of L 1 , L 2 and L 3 is OR or halogen;

[0091] R is selected from the group consisting of H, a straight-chain alkyl group having 1 to 30 carbon atoms, a branched-chain alkyl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms and an aryl group having 6 to 20 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- substitution, and one or more H atoms are optionally substituted by F;

[0092] R 1 and R 2 are the same as or different from each other and each independently selected from H, alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms and aryl having 6 to 20 carbon atoms, wherein one or more H atoms are optionally substituted by F, or R 1 and R 2 together form a monocyclic or polycyclic organic ring system, wherein one or more H atoms are optionally substituted by F;

[0093] Z represents a straight-chain alkylene having 1 to 20 carbon atoms, a branched alkylene having 3 to 20 carbon atoms or a cyclic alkylene having 3 to 20 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally substituted by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C- substitution, and one or more H atoms are optionally substituted by F;

[0094] Y 1 and Y 2 are the same as or different from each other and each independently selected from H, F, Cl and CN;

[0095] R 0 and R 00 are the same as or different from each other and each independently selected from H, straight-chain alkyl having 1 to 20 carbon atoms and branched alkyl having 3 to 20 carbon atoms, and these groups are optionally fluorinated; and wherein

[0096] the second siloxane monomer is different from the first siloxane monomer.

[0097] Preferably, L 1 , L 2 and L 3 are the same as or different from each other and each independently selected from R, OR, F, Cl, Br and I, wherein L 1 , L 2 and L 3At least one of them is OR, F, Cl, Br or I.

[0098] More preferably, one of conditions (1) or (2) applies:

[0099] (1) L 1 = L 2 = L 3 = OR; or

[0100] (2) L 1 = L 2 = R, and L 3 = Cl.

[0101] In a preferred embodiment, R is selected from the group consisting of H, a straight-chain alkyl group having 1 to 20 (preferably 1 to 12) carbon atoms, a branched-chain alkyl group having 3 to 20 (preferably 3 to 12) carbon atoms, a cycloalkyl group having 3 to 20 (preferably 3 to 12) carbon atoms, and an aryl group having 6 to 14 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 = CR 00 -, -CY 1 = CY 2 - or -C≡C-, and one or more H atoms are optionally replaced by F.

[0102] In a more preferred embodiment, R is selected from the group consisting of H, a straight-chain alkyl group having 1 to 12 carbon atoms, a branched-chain alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 14 carbon atoms.

[0103] In the most preferred embodiment, R is selected from the group consisting of H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C6H 11 and -Ph.

[0104] In a preferred embodiment, R 1 and R 2 are the same as or different from each other and are each independently selected from H, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 14 carbon atoms, wherein one or more H atoms are optionally replaced by F, or R 1 and R 2Together form a mono- or polycyclic aliphatic ring system, a mono- or polycyclic aromatic ring system or a polycyclic aliphatic and aromatic ring system, wherein one or more H atoms are optionally replaced by F.

[0105] Preferred mono- or polycyclic aliphatic ring systems have from 3 to 20, preferably 5 to 12, ring carbon atoms. Preferred mono- or polycyclic aromatic ring systems have from 5 to 20, preferably 6 to 12, ring carbon atoms. Preferred polycyclic aliphatic and aromatic ring systems have from 6 to 30, preferably 10 to 20, ring carbon atoms.

[0106] In a more preferred embodiment, R 1 and R 2 are the same or different from each other and are selected from H, -CH3, -CF3, -CH2CH3, -CF2CF3, -CH2CH2CH3, -CH(CH3)2 or -Ph.

[0107] In an even more preferred embodiment, R 1 and R 2 are the same and are selected from -CH3, -CF3, -CH2CH3, -CF2CF3 or -Ph.

[0108] In the most preferred embodiment, R 1 and R 2 are -CH3.

[0109] In a preferred embodiment, Z represents a straight-chain alkylene having 1 to 12 carbon atoms, a branched alkylene having 3 to 12 carbon atoms or a cyclic alkylene having 3 to 12 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C-, and wherein one or more H atoms are optionally replaced by F.

[0110] In a more preferred embodiment, Z represents a straight-chain alkylene having 1 to 12 carbon atoms, which is selected from -(CH2)-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, -(CH2) 10 -, -(CH2) 11 - and -(CH2) 12 -.

[0111] In a preferred embodiment, R 0 and R 00 are the same as or different from each other and each independently selected from H, a straight-chain alkyl group having 1 to 12 carbon atoms, and a branched-chain alkyl group having 3 to 12 carbon atoms, and these groups are optionally fluorinated.

[0112] In a more preferred embodiment, R 0 and R 00 are the same as or different from each other and each independently selected from H, -CH3, -CF3, -CH2CH3, and -CF2CF3.

[0113] In a particularly preferred embodiment, the first repeating unit is derived from a first siloxane monomer represented by the following formula (2):

[0114]

[0115] wherein:

[0116] L 1 = -OCH3, -OCF3, -OCH2CH3, -OCF2CF3, -OCH2CH2CH3, -OCH(CH3)2, -OC6H 11 or -Ph;

[0117] Z = -(CH2) n -, where n = 1 to 10; and

[0118] R 1 = H, -CH3, -CF3, -CH2CH3, -CF2CF3 or -Ph.

[0119] In a most preferred embodiment, the first repeating unit is derived from a first siloxane monomer represented by the following formula (3) or (4):

[0120]

[0121] Second repeating unit

[0122] In a preferred embodiment, the second repeating unit is derived from a second siloxane monomer that does not contain a maleimide group and is represented by one of the following structures S1 or S2:

[0123]

[0124] wherein:

[0125] L 11 、L 12 and L 13 are the same as or different from each other and each independently selected from OR' and halogen;

[0126] R’ is selected from the group consisting of straight-chain alkyl groups having 1 to 30 carbon atoms, branched-chain alkyl groups having 3 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms, and aryl groups having 6 to 20 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 -, or -C≡C-, and wherein one or more H atoms are optionally replaced by F;

[0127] R 11 and R 12 are the same as or different from each other and are each independently selected from the group consisting of H, straight-chain alkyl groups having 1 to 30 carbon atoms, branched-chain alkyl groups having 3 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms, and aryl groups having 6 to 20 carbon atoms, and these groups optionally contain one or more functional groups selected from -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CR 0 =CR 00 2-, -CY 1 =CY 2 -, and -C≡C-, and wherein one or more H atoms are optionally replaced by F; and R 0 、R 00 、Y 1 and Y 2 are defined as shown above.

[0128] Preferably, L 11 、L 12 and L 13 are the same as or different from each other and are each independently selected from OR’, F, Cl, Br, and I.

[0129] More preferably, L 11 、L 12 and L 13 are the same as or different from each other and are each independently selected from OR’.

[0130] In a preferred embodiment, R' is selected from the group consisting of straight-chain alkyl groups having 1 to 20 (preferably 1 to 12) carbon atoms, branched-chain alkyl groups having 3 to 20 (preferably 3 to 12) carbon atoms, cycloalkyl groups having 3 to 20 (preferably 3 to 12) carbon atoms, and aryl groups having 6 to 14 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 -, or -C≡C-, and wherein one or more H atoms are optionally replaced by F.

[0131] In a more preferred embodiment, R' is selected from the group consisting of straight-chain alkyl groups having 1 to 12 carbon atoms, branched-chain alkyl groups having 3 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and aryl groups having 6 to 14 carbon atoms.

[0132] In a particularly preferred embodiment, R' is selected from the group consisting of -CH3, -CF3, -C2H5, -C2F5, -C3H7, -C3F7, -C4H9, -C4F9, -C5H 11 -, -C5H4F7, -C6H 13 -, -C6H4F9, -C7H 15 -, -C7H4F 11 -, -C8H 17 -, -C8H4F 13 -, -CH=CH2, -C(CH3)=CH2, -C6H5, and -C6F5.

[0133] In a most preferred embodiment, R' is selected from -CH3 or -C2H5.

[0134] In a preferred embodiment, R 11 and R 12 are the same as or different from each other and each independently selected from the group consisting of H, straight-chain alkyl groups having 1 to 20 (preferably 1 to 12) carbon atoms, branched-chain alkyl groups having 3 to 20 (preferably 3 to 12) carbon atoms, cycloalkyl groups having 3 to 20 (preferably 3 to 12) carbon atoms, and aryl groups having 6 to 14 carbon atoms, and these groups optionally contain one selected from -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0R 00 -, -CF2-, -CR 0 =CR 00 -, -CR 0 =CR 00 2-, -CY 1 =CY 2 one or more functional groups of - and -C≡C-, and one or more H atoms are optionally replaced by F.

[0135] In a more preferred embodiment, R 11 and R 12 are selected from the group consisting of H, a straight-chain alkyl group having 1 to 12 carbon atoms, a branched-chain alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and these groups optionally contain one or more functional groups selected from -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CR 0 =CR 00 -, -CR 0 =CR 00 2- and -CY 1 =CY 2 -, and one or more H atoms are optionally replaced by F.

[0136] In a particularly preferred embodiment, R 11 and R 12 are selected from the group consisting of -CH3, -CF3, -C2H5, -C2F5, -C3H7, -C3F7, -C4H9, -C4F9, -C5H 11 , -C5H4F7, -C6H 13 , -C6H4F9, -C7H 15 , -C7H4F 11 , -C8H 17 , -C8H4F 13 , -CH=CH2, -C(CH3)=CH2, -C3H6-O-C(=O)-CH=CH2, -C3H6-O-C(=O)-C(CH3)=CH2, -C6H5 and -C6F5.

[0137] In the most preferred embodiment, R 11 and R 12 are selected from -CH3 or -C2H5.

[0138] In a particularly preferred embodiment, the second repeating unit is derived from a second siloxane monomer represented by the following structure S1:

[0139]

[0140] Wherein:

[0141] L 11 、L 12 and L 13 are the same as or different from each other and are each independently selected from OR';

[0142] R' is selected from the group consisting of a straight chain alkyl group having 1 to 20 (preferably 1 to 12) carbon atoms, a branched chain alkyl group having 3 to 20 (preferably 3 to 12) carbon atoms, a cycloalkyl group having 3 to 20 (preferably 3 to 12) carbon atoms, and an aryl group having 6 to 14 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally substituted by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -、-SiR 0 R 00 -、-CF2-、-CR 0 =CR 00 -、-CY 1 =CY 2 - or -C≡C-, and wherein one or more H atoms are optionally replaced by F.

[0143] R 11 is selected from the group consisting of H, a straight-chain alkyl group having 1 to 20 (preferably 1 to 12) carbon atoms, a branched-chain alkyl group having 3 to 20 (preferably 3 to 12) carbon atoms, a cycloalkyl group having 3 to 20 (preferably 3 to 12) carbon atoms, and an aryl group having 6 to 14 carbon atoms, these groups optionally containing an alkyl radical selected from -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -、-SiR 0 R 00 -、-CF2-、-CR 0 =CR 00 -、-CR 0 =CR 00 2-、-CY 1 =CY 2 - and one or more functional groups of -C≡C-, wherein one or more H atoms are optionally replaced by F; and

[0144] R 0 , R 00 , Y 1 and Y 2 Defined as shown above.

[0145] Particularly preferably, in structure S1, the following applies:

[0146] R’ is selected from the group consisting of straight-chain alkyl groups having 1 to 12 carbon atoms, branched-chain alkyl groups having 3 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and aryl groups having 6 to 14 carbon atoms; and R 11 is selected from the group consisting of -CH3, -CF3, -C2H5, -C2F5, -C3H7, -C3F7, -C4H9, -C4F9, -C5H 11 , -C5H4F7, -C6H 13 , -C6H4F9, -C7H 15 , -C7H4F 11 , -C8H 17 , -C8H4F 13 , -CH=CH2, -C(CH3)=CH2, -C3H6-O-C(=O)-CH=CH2, -C3H6-O-C(=O)-C(CH3)=CH2, -C6H5 and -C6F5.

[0147] Preferably, the second siloxane monomer is represented by one of the following structures:

[0148]

[0149] wherein:

[0150] R 11 and R 12 have one of the meanings defined above.

[0151] More preferably, the second siloxane monomer is represented by one of the following structures:

[0152]

[0153]

[0154]

[0155] and

[0156] The third repeating unit

[0157] In a preferred embodiment, the siloxane polymer comprised in the positive photoresist formulation according to the invention further comprises a third repeating unit, wherein the third repeating unit does not contain a maleimide group.

[0158] Preferably, the third repeating unit is different from the second repeating unit.

[0159] In a preferred embodiment, the third repeating unit is derived from a third siloxane monomer represented by one of the following structures T1 or T2:

[0160]

[0161] Wherein:

[0162] L 21 、L 22 、L 23 and L 24 are the same as or different from each other and are each independently selected from OR” and halogen;

[0163] R” is selected from the group consisting of a straight-chain alkyl group having 1 to 30 carbon atoms, a branched-chain alkyl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and an aryl group having 6 to 20 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C-, and one or more H atoms are optionally replaced by F;

[0164] Z is absent or represents a straight-chain alkylene group having 1 to 20 carbon atoms, a branched-chain alkylene group having 3 to 20 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C-, and one or more H atoms are optionally replaced by F; and

[0165] R 0 、R 00 、Y 1 and Y 2 are defined as shown above.

[0166] Preferably, L 21 、L 22 、L 23 and L 24 are the same as or different from each other and are each independently selected from OR”, F, Cl, Br, and I.

[0167] More preferably, L 21 , L 22 , L 23 and L 24 are the same as or different from each other and are each independently selected from OR”.

[0168] For R”, the preferred, more preferred, particularly preferred and most preferred definitions disclosed above for R’ are correspondingly applicable.

[0169] In a preferred embodiment, Z is absent or represents a straight-chain alkylene group having 1 to 12 carbon atoms, a branched-chain alkylene group having 3 to 12 carbon atoms or a cyclic alkylene group having 3 to 12 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C-, and wherein one or more H atoms are optionally replaced by F, wherein R 0 , R 00 , Y 1 and Y 2 are defined as shown above.

[0170] In a more preferred embodiment, Z is absent or represents a straight-chain alkylene group having 1 to 12 carbon atoms, which is selected from -(CH2)-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, -(CH2) 10 -, -(CH2) 11 - and -(CH2) 12 -.

[0171] In a particularly preferred embodiment, the third repeating unit is derived from a third siloxane monomer represented by the following structure T1:

[0172]

[0173] Wherein:

[0174] L 21 , L 22 , L 23 and L 24 are the same as or different from each other and are each independently selected from OR”;

[0175] R" is selected from the group consisting of a straight-chain alkyl group having 1 to 20 (preferably 1 to 12) carbon atoms, a branched-chain alkyl group having 3 to 20 (preferably 3 to 12) carbon atoms, a cycloalkyl group having 3 to 20 (preferably 3 to 12) carbon atoms, and an aryl group having 6 to 14 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally substituted by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -、-SiR 0 R 00 -、-CF2-、-CR 0 =CR 00 -、-CY 1 =CY 2 - or -C≡C-, and wherein one or more H atoms are optionally replaced by F; and

[0176] R 0 , R 00 , Y 1 and Y 2 Defined as shown above.

[0177] In an alternative particularly preferred embodiment, the third repeating unit is derived from a third siloxane monomer represented by the following structure T2:

[0178]

[0179] in

[0180] L 21 , L 22 and L 23 are the same as or different from each other and are independently selected from OR";

[0181] R" is selected from the group consisting of a straight-chain alkyl group having 1 to 20 (preferably 1 to 12) carbon atoms, a branched-chain alkyl group having 3 to 20 (preferably 3 to 12) carbon atoms, a cycloalkyl group having 3 to 20 (preferably 3 to 12) carbon atoms, and an aryl group having 6 to 14 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally substituted by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -、-SiR 0 R 00 -、-CF2-、-CR 0 =CR 00 -、-CY 1 =CY 2 - or -C≡C-, and wherein one or more H atoms are optionally replaced by F;

[0182] Z is absent or represents a straight-chain alkylene group having 1 to 12 carbon atoms, a branched-chain alkylene group having 3 to 12 carbon atoms, or a cyclic alkylene group having 3 to 12 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 -, or -C≡C-, and wherein one or more H atoms are optionally replaced by F; and R 0 , R 00 、Y 1 [[ID=2'1]]and Y 2 are defined as shown above.

[0183] The preferred third siloxane monomer is represented by one of the following structures:

[0184]

[0185] wherein:

[0186] L 21 and Z have one of the meanings defined above. [[ID=]38]

[0187] The more preferred third siloxane monomer is represented by one of the following structures:

[0188]

[0189]

[0190] and

[0191] The molar fractions of the first, second, and third repeating units

[0192] Preferably, the molar fraction of the first repeating unit in the siloxane polymer is in the range of 1 to 90%, preferably 5 to 70%, more preferably 10 to 50%, even more preferably 10 to 40%, and most preferably 10 to 30%, based on the total amount of repeating units in the siloxane polymer.

[0193] Preferably, the mole fraction of the second repeating unit in the silicone polymer ranges from 10 to 90%, preferably from 30 to 80%, more preferably from 40 to 60%, even more preferably from 45 to 55%, and most preferably 50%, based on the total amount of repeating units in the silicone polymer.

[0194] Further preferably, the mole fraction of the first repeating unit in the silicone polymer ranges from 1 to 90%, preferably from 5 to 70%, more preferably from 10 to 50%, even more preferably from 10 to 40%, and most preferably from 10 to 30%, and the mole fraction of the second repeating unit in the silicone polymer ranges from 10 to 90%, preferably from 30 to 80%, more preferably from 40 to 60%, even more preferably from 45 to 55%, and most preferably 50%, based on the total amount of repeating units in the silicone polymer.

[0195] Preferably, the mole fraction of the third repeating unit in the silicone polymer ranges from 0 to 50%, preferably from 5 to 40%, more preferably from 10 to 30%, and most preferably from 20 to 30%, based on the total amount of repeating units in the silicone polymer.

[0196] Further preferably, the mole fraction of the first repeating unit in the silicone polymer ranges from 1 to 90%, preferably from 5 to 70%, more preferably from 10 to 50%, even more preferably from 10 to 40%, and most preferably from 10 to 30%, and the mole fraction of the second repeating unit in the silicone polymer ranges from 10 to 90%, preferably from 30 to 80%, more preferably from 40 to 60%, even more preferably from 45 to 55%, and most preferably 50%, and the mole fraction of the third repeating unit in the silicone polymer ranges from 0 to 50%, preferably from 5 to 40%, more preferably from 10 to 30%, and most preferably from 20 to 30%, based on the total amount of repeating units in the silicone polymer.

[0197] The mole fractions of the repeating units present in the silicone polymer add up to 100%.

[0198] Additional repeating units

[0199] In a preferred embodiment, the silicone polymer comprised in the positive photoresist formulation according to the invention further comprises one or more additional repeating units, wherein the one or more additional repeating units do not contain maleimide groups.

[0200] Preferably, the one or more additional repeating units are different from the second repeating unit and the third repeating unit.

[0201] In a preferred embodiment, the one or more additional repeating units are derived from one or more additional siloxane monomers represented by the following structure F1:

[0202]

[0203] Wherein:

[0204] L 31 、L 32 and L 33 are the same as or different from each other and are each independently selected from OR”’ and halogen;

[0205] R”’ is selected from the group consisting of straight-chain alkyl groups having 1 to 30 carbon atoms, branched-chain alkyl groups having 3 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms, and aryl groups having 6 to 20 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C-, and wherein one or more H atoms are optionally replaced by F;

[0206] R 31 is selected from the group consisting of H, straight-chain alkyl groups having 1 to 30 carbon atoms, branched-chain alkyl groups having 3 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms, and aryl groups having 6 to 20 carbon atoms, and these groups optionally contain one or more functional groups selected from -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CR 0 =CR 00 2-, -CY 1 =CY 2 - and -C≡C-, and wherein one or more H atoms are optionally replaced by F; and

[0207] R 0 、R 00 、Y 1 and Y 2 are defined as shown above.

[0208] Preferably, L 31 、L 32 and L 33 are the same as or different from each other and are each independently selected from OR”’, F, Cl, Br, and I.

[0209] More preferably, L 31 、L 32 and L 33 are the same as or different from each other and are each independently selected from OR”’.

[0210] For R”’, the preferred, more preferred, particularly preferred, and most preferred definitions disclosed above for R’ apply correspondingly.

[0211] In a preferred embodiment, R 31 is selected from the group consisting of H, a straight-chain alkyl having 1 to 20 (preferably 1 to 12) carbon atoms, a branched-chain alkyl having 3 to 20 (preferably 3 to 12) carbon atoms, a cycloalkyl having 3 to 20 (preferably 3 to 12) carbon atoms, and an aryl having 6 to 14 carbon atoms, and these groups optionally contain one or more functional groups selected from -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CR 0 =CR 00 2-, -CY 1 =CY 2 -, and -C≡C-, and one or more H atoms are optionally replaced by F.

[0212] In a more preferred embodiment, R 31 is selected from the group consisting of H, a straight-chain alkyl having 1 to 12 carbon atoms, a branched-chain alkyl having 3 to 12 carbon atoms, a cycloalkyl having 3 to 12 carbon atoms, and an aryl having 6 to 14 carbon atoms, and these groups optionally contain one or more functional groups selected from -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CR 0 =CR 00 -, -CR 0 =CR 00 2-, and -CY 1 =CY 2 -, and one or more H atoms are optionally replaced by F.

[0213] In a particularly preferred embodiment, R 31Selected from the group consisting of -CH3, -CF3, -C2H5, -C2F5, -C3H7, -C3F7, -C4H9, -C4F9, -C5H 11 , -C5H4F7, -C6H 13 , -C6H4F9, -C7H 15 , -C7H4F 11 , -C8H 17 , -C8H4F 13 , -CH=CH2, -C(CH3)=CH2, -C3H6-O-C(=O)-CH=CH2, -C3H6-O-C(=O)-C(CH3)=CH2, -C6H5 and -C6F5.

[0214] In a most preferred embodiment, R 31 is selected from -C6H5 and -C6F5.

[0215] Preferably, the additional siloxane monomer is represented by one of the following structures:

[0216]

[0217] wherein: R 31 has one of the meanings defined above.

[0218] More preferably, the additional siloxane monomer is represented by one of the following structures: and

[0219] Preferably, the mole fraction of the one or more additional repeating units in the siloxane polymer is in the range of 0 to 50%, preferably 5 to 40%, more preferably 10 to 30%, and most preferably 20 to 30%, based on the total amount of repeating units in the siloxane polymer.

[0220] The mole fraction of the one or more additional repeating units, added to the mole fractions of the first repeating unit, the second repeating unit, and optionally the third repeating unit present in the siloxane polymer, is 100%.

[0221] Chemical and physical characteristics of the siloxane polymer

[0222] The expression "derived from a specific siloxane monomer" means that the relevant repeating unit of the siloxane polymer is formed by the condensation reaction of the specific siloxane monomer with another monomer, usually while retaining the characteristic structural features of the relevant repeating unit of the specific siloxane monomer in the part of the siloxane polymer being formed.

[0223] The siloxane polymer used in the present invention can have a linear and / or branched structure. Branched structures include, for example, ladder, closed cage, open cage, and amorphous structures.

[0224] Preferably, the siloxane polymer for use in the present invention has a molecular weight M of at least 500 g / mol, more preferably at least 1,000 g / mol, even more preferably at least 2,000 g / mol w , as determined by GPC. Preferably, the molecular weight M of the siloxane oligomer or polymer w is less than 50,000 g / mol, more preferably less than 30,000 g / mol, even more preferably less than 10,000 g / mol.

[0225] Effect of repeating units in the siloxane polymer

[0226] The first repeating unit increases pattern characteristics and reduces flow during the overall exposure and post-baking processes (see Figure 1 , steps IV and V). In addition, it increases pattern flexibility.

[0227] The second repeating unit allows for the adjustment of certain properties of the photoresist formulation, such as, for example, the alkali dissolution rate (ADR), molecular weight distribution, thermal properties, and mechanical properties.

[0228] The presence of the third repeating unit in the siloxane polymer reduces flow and increases pattern characteristics during the overall exposure and post-baking processes (see Figure 1 , steps IV and V). In addition, it increases the mechanical properties of the pattern.

[0229] The presence of one or more additional repeating units allows for the fine-tuning of certain properties of the photoresist formulation, such as mechanical properties, dissolution rate, etc.

[0230] Photoactive dissolution regulator

[0231] The positive photoresist formulation according to the present invention contains a photoactive dissolution regulator. The photoactive dissolution regulator is a compound that converts the photoresist into a derivative soluble in a suitable developer upon exposure to light. During the masking and patterning of the positive photoresist, a portion of the photoresist film is exposed to light while the other remains unexposed. In the unexposed areas, the photoresist remains insoluble in the developer, while in the exposed areas, the photoactive dissolution regulator forms a soluble substance that enables the photoresist to dissolve in the developer.

[0232] In the present invention, the photoactive dissolution regulator converts the siloxane polymer into a derivative soluble in the developer upon exposure to light.

[0233] Preferably, the photoactive dissolution regulator is selected from the list consisting of diazonaphthoquinone (DNQ) or its derivatives. Here, the diazonaphthoquinone derivative is a compound prepared by esterification of naphthoquinone diazide sulfonic acid with a compound having a phenolic hydroxyl group, but is not limited particularly in terms of structure, and is preferably an ester compound and a compound having one or more phenolic hydroxyl groups. As the naphthoquinone diazide sulfonic acid, 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid can be used. Due to the absorption in the i-line (wavelength: 365 nm) region, 4-naphthoquinone diazide sulfonic acid ester compounds are suitable for i-line exposure. In addition, due to the absorption in a wide range of wavelength regions, 5-naphthoquinone diazide sulfonic acid ester compounds are suitable for exposure to a wide range of wavelengths. Depending on the exposure wavelength, preferably 4-naphthoquinone diazide sulfonic acid ester compounds or 5-naphthoquinone diazide sulfonic acid ester compounds are selected. A mixture of 4-naphthoquinone diazide sulfonic acid ester compounds and 5-naphthoquinone diazide sulfonic acid ester compounds can also be used.

[0234] The compound having a phenolic hydroxyl group is not particularly limited, but includes, for example, the following compounds (trade name, manufactured by Honshu Chemical Industry Co., Ltd.):

[0235]

[0236]

[0237] A particularly preferred diazonaphthoquinone derivative is 4,4'-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol (TrisP-PA) modified with 2.0 moles of naphthoquinone diazide sulfonic acid.

[0238] Although the optimal amount depends on the esterification rate of naphthoquinone diazide sulfonic acid or the properties of the polysiloxane used, the required sensitivity, and the change in dissolution contrast between the exposed part and the unexposed part, the addition amount of the diazonaphthoquinone derivative is preferably 3 to 20% by weight, more preferably 5 to 15% by weight, based on the total weight of the silicone polymer. If the addition amount of the diazonaphthoquinone derivative is 3% by weight or more, the dissolution contrast between the exposed part and the unexposed part becomes high and good photosensitivity is obtained. In addition, to obtain a more preferred dissolution contrast, it is preferably 5% by weight or more. On the other hand, when the amount of the diazonaphthoquinone derivative is 20% by weight or less, the colorless transparency of the cured film is improved.

[0239] Additional components

[0240] Preferably, the positive photoresist formulation according to the present invention contains one or more additional silicone polymers, wherein the additional silicone polymer does not contain a maleimide group.

[0241] Preferably, the positive photoresist formulation according to the present invention comprises one or more solvents. Examples of such solvents include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; propylene glycol alkyl ether acetates such as PGMEA, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, etc. These solvents are used separately alone or in combination of two or more of them. The blending ratio of the solvents varies depending on the coating method or the requirement for the film thickness after coating.

[0242] Preferred solvents are polar solvents such as, for example, alcohol solvents and ester solvents. Preferred alcohol solvents are ethanol, propan-1-ol, propan-2-ol, and propylene glycol methyl ether (PGME). Preferred ester solvent is 1-methoxy-2-propyl acetate (PGMEA).

[0243] The positive photoresist formulation may further contain a surfactant. The use of a surfactant can preferably improve the coating properties. Surfactants that can be used include nonionic surfactants, anionic surfactants, amphoteric surfactants, etc.

[0244] Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diesters; polyoxyethylene fatty acid monoesters; polyoxyethylene-polyoxypropylene block copolymers; alkynols; alkynediols; polyethoxylates of alkynols; alkynediol derivatives such as polyethoxylates of alkynediols; fluorosurfactants, for example, FLUORAD (trade name, manufactured by Sumitomo 3M Limited), MEGAFAC (trade name, manufactured by DIC Cooperation), SURFLON (trade name, manufactured by Asahi Glass Co., Ltd.); or silicone surfactants, for example, KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Examples of such alkynediols include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyn-3,6-diol, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyn-2,5-diol, 2,5-dimethyl-2,5-hexanediol, etc.

[0245] Examples of anionic surfactants include ammonium salts or organic amine salts of alkyl diphenyl ether disulfonic acid, ammonium salts or organic amine salts of alkyl diphenyl ether sulfonic acid, ammonium salts or organic amine salts of alkyl benzene sulfonic acid, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfuric acid, ammonium salts or organic amine salts of alkyl sulfuric acid, etc.

[0246] Examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolium betaine, lauric acid amide propyl hydroxy sulfone betaine, etc.

[0247] These surfactants can be used alone or in combination of two or more of them, and their blending ratio is usually 50 to 10,000 ppm, preferably 100 to 5,000 ppm, based on the total mass of the silicone composition.

[0248] Preferably, the positive photoresist formulation contains one or more initiators, such as, for example, a photochemically activated initiator or a thermally activated initiator. Preferred photochemically activated initiators are photoinitiators that generate reactive species (such as, for example, free radicals, cations or anions) when exposed to radiation (such as, for example, UV or visible light). Suitable photoinitiators are, for example, the Omnipol series (such as Omnipol TX) and the Speedcure series (such as Speedcure 7010). Preferred thermally activated initiators are thermally activated initiators that generate reactive species (such as, for example, free radicals, cations or anions) when exposed to heat.

[0249] The addition of Omnipol TX allows irradiation at a longer wavelength of about 365 nm compared to about 254 nm for the standard formulation for curing.

[0250] In a particularly preferred embodiment of the present invention, the positive photoresist formulation contains a photoinitiator.

[0251] The total amount of the initiator in the positive photoresist formulation is preferably in the range of 0.01 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total weight of the silicone polymer.

[0252] Further preferably, the positive photoresist formulation does not contain a photoacid generator (PAG). However, if PAG is required for other purposes, PAG includes diazomethane compounds, triazine compounds, sulfonic acid esters, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, phosphonium salts, sulfonimide compounds, etc.

[0253] The positive photoresist formulation may further comprise a curing accelerator. As the curing accelerator, a thermal acid generator or a thermal base generator can be used. Examples of thermal acid generators include salts or esters capable of generating organic acids, such as various aliphatic sulfonic acids and their salts, various aliphatic carboxylic acids (such as citric acid, acetic acid, and maleic acid) and their salts, various aromatic carboxylic acids (such as benzoic acid and phthalic acid) and their salts, aromatic sulfonic acids and their ammonium salts, various amine salts, aromatic diazonium salts, and phosphonic acids and their salts. Among the thermal acid generators, in particular, salts composed of organic acids and organic bases are preferred and salts composed of sulfonic acids and organic bases are more preferred.

[0254] Preferred sulfonic acids include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, etc. These acid generators can be used alone or in combination.

[0255] Examples of thermal base generators include compounds that generate bases (such as imidazole, tertiary amines, and quaternary amines) and their mixtures. Examples of the bases to be released include imidazole derivatives, such as N-(2-nitrobenzyloxycarbonyl)imidazole, N-(3-nitrobenzyloxycarbonyl)imidazole, N-(4-nitrobenzyloxycarbonyl)imidazole, N-(5-methyl-2-nitrobenzyloxycarbonyl)imidazole, N-(4-chloro-2-nitrobenzyloxycarbonyl)imidazole, and 1,8-diazabicyclo[5.4.0]undec-7-ene. Like the acid generators, these base generators can be used alone or in combination.

[0256] Preferably, the positive photoresist formulation further comprises one or more inorganic filler materials. Preferred inorganic filler materials are selected from nitrides, titanates, diamonds, oxides, sulfides, sulfites, sulfates, silicates, and carbides, which may optionally be surface-modified with capping agents. More preferably, the filler material is selected from the list consisting of AlN, Al2O3, BN, BaTiO3, B2O3, Fe2O3, SiO2, TiO2, ZrO2, PbS, SiC, diamond, and glass particles.

[0257] Preferably, the total content of the inorganic filler material in the positive photoresist formulation is in the range of 0.001 to 90% by weight, more preferably 0.01 to 70% by weight, and most preferably 0.01 to 50% by weight, based on the total weight of the composition.

[0258] The positive photoresist formulation of the present invention may comprise one or more additives selected from diamines, diols, dicarboxylic acids, polyhedral oligomeric silsesquioxanes (POSS), edge-modified silsesquioxanes, small aromatic or aliphatic compounds, and nanoparticles, which may optionally be modified with maleimide or dimethylmaleimide groups.

[0259] The modified POSS compounds can be readily prepared from available precursors and readily incorporated into the crosslinkable compositions under suitable mixing conditions. For example, maleimide-substituted POSS compounds and their preparation methods are described in US 2006 / 0009578 A1, the disclosure of which is incorporated herein by reference.

[0260] Preferred additives are selected from:

[0261]

[0262]

[0263]

[0264]

[0265] wherein:

[0266]

[0267] X = -OH, -NH2, -CO2H or

[0268] Sp = -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- or -Si(CH3)2-CH2-CH2-CH2-;

[0269] R x = H, -CH3, CF3, CN or -CH2CH3; and

[0270] n = 1 to 36, preferably 1 to 20, more preferably 1 to 12.

[0271] Method for manufacturing a microelectronic structure

[0272] In a second aspect, the present invention provides a method for manufacturing a microelectronic structure, preferably an encapsulated microelectronic structure, FET structure or TFT structure, which comprises the following steps:

[0273] (1) Applying a positive photoresist formulation according to the present invention to the surface of a substrate, preferably to the surface of a conductor or semiconductor substrate;

[0274] (2) Photopatterning the positive photoresist formulation applied in step (1), preferably by (2a) irradiating the applied positive photoresist formulation with light of a specific wavelength through a mask, and (2b) developing the irradiated positive photoresist formulation by exposing it to a developer and a washing liquid to obtain a photopatterned structure; and

[0275] (3) Cure the optically patterned structure obtained in step (2), preferably by (3a) exposing the optically patterned structure to UV light irradiation, and (3b) subjecting it to a post-baking treatment to obtain a cured optically patterned dielectric material on the substrate surface.

[0276] The cured optically patterned dielectric material on the substrate surface preferably passivates and optionally planarizes the substrate surface.

[0277] Preferably, the substrate surface to which the positive photoresist formulation is applied in step (1) can be made of different materials, such as, for example, conductor or semiconductor materials, passivation, protection or planarization layers, etc. Preferred conductor materials are metals such as, for example, aluminum, molybdenum, titanium, nickel, copper, silver, metal alloys, and the like. Preferred semiconductor materials are metal oxides such as indium gallium zinc oxide (IGZO), indium zinc oxide (IZO), or amorphous silicon and polycrystalline silicon. Preferred passivation, protection or planarization layers can be prepared from any polymer material (e.g., polyimide, polybenzylcyclobutane, silicon nitride, silicon oxynitride, silicon oxide, silicon carbide, etc.).

[0278] Preferably, the positive photoresist formulation applied in step (1) contains one or more initiators. Preferred initiators are those described above.

[0279] When the positive photoresist formulation contains a solvent, preferably the formulation has a certain concentration of silicone polymer, depending on the desired film thickness. To adjust the concentration of the silicone polymer, the solvent is removed by heating, more preferably by heating to 80 to 120 °C. The preferred concentration of the silicone polymer ranges from 1 to 50 wt%, more preferably 10 to 40 wt%, and most preferably 20 to 30 wt%, based on the total weight of the silicone polymer and the solvent in the formulation.

[0280] The method of applying the positive photoresist formulation in step (1) is not particularly limited. The preferred application methods for step (1) are dispensing, dipping, screen printing, stencil printing, roll coating, spraying, slot coating, slit coating, spin coating, stereolithography, gravure printing, flexographic printing, or inkjet printing.

[0281] The positive photoresist formulation of the present invention can be provided in the form of formulations suitable for gravure printing, flexographic printing, and / or inkjet printing. For preparing these formulations, ink-based formulations known from the prior art can be used.

[0282] Preferably, the positive photoresist formulation is applied in step (1) as a layer having an average thickness of about 0.1 to 50 μm, more preferably about 0.5 to 20 μm, and most preferably about 1 to 5 μm. The desired layer thickness can be obtained by applying the positive photoresist formulation with various concentrations by single or multiple applications.

[0283] Preferably, the positive photoresist formulation applied to the substrate surface in step (1) is cured by a pre-baking treatment. This pre-baking preferably cures the positive photoresist formulation on the substrate. The pre-baking treatment can be carried out at a temperature of 70 to 150 °C, preferably at a temperature of 90 to 130 °C. The time of the pre-baking treatment is preferably between 10 and 180 seconds, more preferably 30 to 90 seconds, in the case of a hot plate, and preferably 1 to 10 minutes, more preferably 1 to 5 minutes, in the case of an oven. It particularly preferably includes a step of removing excess solvent by rotation or vacuum before the pre-baking treatment.

[0284] Preferably, the photolithography in step (2) is carried out by: (2a) irradiating the applied positive photoresist formulation with light of a specific wavelength through a mask, and (2b) developing the irradiated positive photoresist formulation by exposing it to a developer and a washing liquid to obtain a photopatterned structure.

[0285] Preferably, the irradiation with light of a specific wavelength in step (2a) involves exposure to UV and / or violet light. Generally, any type of light source commonly used in the patterning process can be used. Such light sources include high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, xenon, etc., laser diodes, LEDs, etc. As UV light, ultraviolet rays such as g-line, h-line, and i-line are usually used. Except for ultra-fine processing (such as for semiconductors), light of 360 to 430 nm (high-pressure mercury lamp) is generally used for patterns of several μm to several tens of μm. Most importantly, in the case of liquid crystal display devices, light of 430 nm is usually used. Although the energy of the irradiated light depends on the light source or the thickness of the positive photoresist layer, it is preferably in the range of 20 to 2,000 mJ / cm 2 ², preferably 50 to 1,000 mJ / cm 2 ².

[0286] To irradiate light in a pattern, a common photomask can be used. Such a photomask can be freely selected from known photomasks. Although the environment during irradiation is not particularly limited, generally it can be an ambient atmosphere (in air) or a nitrogen atmosphere. Additionally, in the case of forming a film on the entire surface of the substrate, the light can be irradiated on the entire surface of the substrate. In the present invention, the patterned structure also includes the case of forming a structure on the entire surface of the substrate.

[0287] As a developer for development, any developer that is usually applied to the development of conventional photosensitive silicone compositions can be used. Preferred developers include alkaline developers that are aqueous solutions of alkaline compounds (such as tetraalkylammonium hydroxides, choline, alkali metal hydroxides, alkali metal metasilicates (hydrates), alkali metal phosphates (hydrates), ammonia, alkylamines, alkanolamines, and heterocyclic amines), and a particularly preferred alkaline developer is an aqueous TMAH solution. These alkaline developers may optionally further contain water-soluble organic solvents (such as methanol and ethanol) or surfactants. The development method can also be freely selected from conventional methods. Generally, it includes methods such as dipping in the developer (immersion), paddle, shower, slit, spin coating, and spraying. A pattern can be obtained through this development. After development with the developer, it is preferably followed by a water rinse.

[0288] Preferably, the curing in step (3) is carried out by: (3a) exposing the photo-patterned structure to UV light irradiation (i.e., full wafer exposure), and (3b) subjecting it to a post-bake heat treatment to obtain a cured photo-patterned dielectric material on the substrate surface.

[0289] When a positive photoresist formulation is used to form a transparent coating, it is necessary to irradiate with light, which is called bleaching or full wafer exposure (3a). By performing full wafer exposure, the unreacted diazonaphthoquinone derivatives remaining in the film are photodecomposed and the light transparency of the film is further improved. In the bleaching exposure method, a high-pressure mercury lamp, a low-pressure mercury lamp, etc. are used, and an exposure irradiation intensity of about 10 to 2,000 mJ / cm 2 is applied over the entire surface.

[0290] Preferably, the post-bake heat treatment in step (3b) involves exposure to heat. The curing temperature of the structure is not particularly limited and can be freely selected as long as the dehydration condensation of the silicone polymer proceeds. When the curing temperature is too low, the reaction does not proceed sufficiently and silanol groups remain in the film, which can adversely affect the coating properties. Therefore, more preferably, the post-bake heat treatment involves exposure to an elevated temperature, preferably in the range of 100 to 300 °C, more preferably 150 to 250 °C, and most preferably 180 to 230 °C.

[0291] Generally, when heating a developed pattern to cure it, the shape of the pattern usually changes. Specifically, the developed pattern generally has a rectangular cross-section and its sidewalls stand almost straight. However, when the pattern is heated, the coated material temporarily softens, and the cross-sectional shape of the pattern tends to change from rectangular to trapezoidal. As a result, by heating, the tilt angle (i.e., the taper angle) of the sidewalls tends to decrease and the cross-sectional bottom width (i.e., the line width) of the pattern tends to increase.

[0292] In contrast, by using the positive photoresist formulation according to the present invention, the reduction of the taper angle due to the flow of the softened material can be suppressed to obtain a comparable taper angle after post-baking (3a) following the development step (2b). It is assumed that this is due to the crosslinking of the siloxane in step (2a).

[0293] Electronic device

[0294] In a third aspect, the present invention provides an electronic device, preferably an encapsulated microelectronic device, an FET array panel or a TFT array panel, which includes a microelectronic structure obtainable by the method for manufacturing a microelectronic structure according to the present invention.

[0295] For the electronic device, preferably, the cured photo-patterned dielectric material obtained from the positive photoresist formulation passivates and optionally planarizes the substrate surface that forms part of the microelectronic structure. The cured photo-patterned dielectric material forms a dielectric layer that is used to electrically isolate one or more electronic components of the electronic device from each other.

[0296] The present invention is further illustrated by the following examples hereinafter, which should not be construed as limiting. Those skilled in the art will recognize that various modifications, additions, and substitutions can be made to the present invention without departing from the spirit and scope of the invention as defined in the appended claims. Examples

[0297] Measurement method

[0298] NMR spectroscopy: The NMR sample was placed inside a 3.7 mm thin-walled precision glass NMR tube (Wilmad 537PPT) (the NMR tube containing CD3CN in the annular space) inside a 5 mm FEP liner or inside a 5 mm precision glass NMR tube as an anhydrous solvent. The measurement was carried out at 25 °C on a Bruker Avance III 400 MHz spectrometer equipped with a 9.3980T cryomagnet. Using a 5 mm combined H / F probe operating at 400.17 and 376.54 MHz respectively, an H NMR spectrum was obtained. Using a 5 mm broadband inverse probe operating at 100.62 and 79.50 MHz respectively, 1 H / 19 F probe operating at 400.17 and 376.54 MHz respectively, an 1 H NMR spectrum was obtained. Using a 5 mm broadband inverse probe operating at 100.62 and 79.50 MHz respectively, 13 C and 29Si NMR spectra. Set the line broadening parameter in the exponential multiplication for free induction decay to be equal to or less than the resolution of its respective data points or the intrinsic linewidth of the resonance. Unless otherwise specified, all line shape functions are Lorentzian. In some cases, the free induction decay is multiplied by a Gaussian function for resolution enhancement of the Fourier transform. Referenced relative to tetramethylsilane (TMS). 1 1H NMR chemical shifts, which produce the following chemical shifts for the solvents used below: CDCl3 (7.23 ppm), DMSO-d6 (2.50 ppm), and CD2HCN (1.96 ppm). Referenced relative to tetramethylsilane (TMS). 13 13C NMR spectra, which use the chemical shifts for the following solvents: CDCl3 (77.2 ppm), DMSO-d6 (39.5 ppm), and CD3 C N (118.7 ppm). Referenced relative to SiCl4 29 Si NMR chemical shifts. A positive (negative) sign indicates a chemical shift at a higher (lower) frequency relative to the reference compound.

[0299] GPC analysis: Gel permeation chromatography (GPC) analysis was performed on a Waters e2695 liquid chromatography system equipped with a refractive index detector. The column was eluted with tetrahydrofuran at a flow rate of 0.6 cm 3 / min and a temperature of 40 °C. A series of 6 narrow-dispersity polystyrene standards were used to calibrate the GPC system.

[0300] Photopatterning: The dried coating film was placed in a NES2W-ghi06 stepper (Nikon Engineering Co., Ltd.; Nikon Precicion inc.) with a line pitch and hole pattern shape (4 μm lines, 12 μm pitch) and exposed to light using broadband illumination to accommodate ghi-line photoresist processing. The stepper uses an exposure wavelength of 365 to 436 nm to deliver a resolution of less than 2.3 μm, with a champion performance of up to 1.7 μm and a wafer size coverage accuracy of 0.35 μm for wafers up to 150 to 200 mm. 2 The UV lamp exposes the entire surface 1: There is a method of exposing the entire surface using an ultraviolet-visible exposure machine (such as a Canon mask aligner model PLA-501F) with approximately 100 to 2000 mJ / cm

[0301] (based on the exposure amount at a wavelength of 365 nm). 2 The entire surface was exposed using an ultraviolet-visible exposure machine (such as a Canon mask aligner model PLA-501F).

[0302] The UV lamp exposes the entire surface 2: There is a method of exposing the entire surface using an ultraviolet-visible exposure machine (e.g., Ushio) with an exposure amount of about 50 to 100 mJ / cm 2 (according to the exposure amount at a wavelength of 230 nm).

[0303] Synthetic monomer

[0304] 1-Allyl-3,4-dimethyl-pyrrole-2,5-dione:

[0305]

[0306] In a 250 mL round-bottom flask equipped with a Dean Stark water separator, 3,4-dimethyl-furan-2,5-dione (160.0 g; 1243.4 mmol; 1.0 eq.) was dissolved in anhydrous toluene (1040 mL; 9.8 mol; 7.90 eq.). The mixture was stirred at room temperature until completely dissolved. At 23 °C, a solution of allylamine (139.9 ml; 1865.0 mmol;

[0307] 1.5 eq.) contained in anhydrous toluene (160.0 ml; 1.5 mol; 1.2 eq.) was added via a dropping funnel. The solution was heated (140 °C, reflux) and stirred at 140 °C for 5 hours. Over time, a white solid precipitated. Subsequently, the mixture was cooled to room temperature and toluene was removed at 70 °C under vacuum (10 mbar). A clear and light orange crude product (222 g) was separated. After fractional condensation at 120 °C under vacuum (10 -2 mbar), a clear and colorless product, 1-allyl-3,4-dimethyl-pyrrole-2,5-dione (201.2 g; 1.169 mmol), was separated with a yield of 94% and a purity of 96%. The product was stored at low temperature (4 °C).

[0308] 1 1H-NMR (400.17 MHz, DMSO, δ, in ppm): 1.92 (s, 6H, CH3); 4.01 (dt, 3 J HH = 5.1 Hz, 4 J HH = 1.7, 2H, CH2); 5.05 (ddt, 3 J trans-HH = 17.1 Hz, 2 J HH = 3.1 Hz, 4 J HH = 1.5 Hz, 1H, CH2=CH); 5.08 (ddt, 3 J cis-HH= 10.3 Hz, 2 J HH = 3.1 Hz, 4 J HH = 1.5 Hz, 1H, CH2=CH); 5.79 (ddt, 3 J trans-HH = 17.1 Hz, 3 J cis-HH = 10.3 Hz, 3 J HH = 5.1 Hz, 1H, CH2=CH).

[0309] 13 C-NMR (100.62 MHz, CDCl3, δ, in ppm): 8.62 (q, 1 J CH = 129.5 Hz, CH3); 39.92 (td, 1 J CH = 140.3 Hz, 2 J CH = 8.0 Hz, 2 J CH = 5.5 Hz, CH2); 117.18 (ddt, 1 J CH = 159.4 Hz, 1 J CH = 155.3 Hz, 3 J CH = 5.5 Hz, CH2); 132.01 (dtd, 1 J CH = 157.7 Hz, 2 J CH = 5.5 Hz, 2 J CH = 3.0 Hz, CH); 137.18 (qq, 2 J CH = 7.5 Hz, 3 J CH = 5.7 Hz, C=C); 171.6 (m, C=O).

[0310] 3,4-Dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (DMMI):

[0311] In a 500 mL round-bottom flask equipped with a reflux condenser, a pale yellow liquid 1-allyl-3,4-dimethyl-pyrrole-2,5-dione (100.0 g; 851.2 mmol; 1.0 eq.) was provided, and platinum(IV) oxide (25.0 mg; 0.110 mmol;

[0312] 1.15 eq.) and triethoxysilane (129.9 g; 668.3 mmol; 1.15 eq.) were added at room temperature with vigorous stirring. The solution was heated to 80 °C and stirred at 80 °C for 190 hours. The completion of the reaction was monitored by 1 1H NMR spectroscopy. Subsequently, the solution was cooled to room temperature. Chloroform (100 mL) and activated carbon (8.0 g) were added and stirred at room temperature for 1 hour. Subsequently, the suspension was filtered (filter paper and 0.45 μm PTFE filter), and the mother liquor was distilled at 60 °C under vacuum (20 mbar) to remove the solvent. The product 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione, which was a transparent and light brown liquid (162 g), was isolated. After fractional condensation at 130 to 140 °C under vacuum (0.2 to 0.35 mbar), the transparent and dark yellow substance β 3,4-dimethyl-1-(2-triethoxysilylpropyl)pyrrole-2,5-dione (11.93 g; 36.2 mmol) was isolated, with a yield of 6.2% and a purity of 96%. The desired product γ 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione, which was a transparent and colorless liquid (147.6 g; 448 mmol), was isolated at 160 °C under vacuum (0.2 mbar), with a yield of 77% and a purity of 99%. This substance was stored at low temperature (4 °C).

[0313] 1 1H-NMR (400.17 MHz, CD3CN film, δ, in ppm): -0.05 (m, 2H, CH2); 0.61 (t, 3 J HH = 7.0 Hz, 9H, CH3); 1.04 (tt, 3 J HH = 7.3 Hz, 3 J HH = resolution τ 1 / 2 = 2.5 Hz, 2H, CH2); 1.36 (s, 6H, CH3); 2.85 (t, 3 J HH = 7.3, 2H, CH2); 3.21 (q, 3 J HH = 7.0 Hz, 6H, CH2).

[0314] 13C-NMR (100.62 MHz, CD3CN film, δ, in ppm): 6.69 (tt, 1 J CH = 117.1 Hz, 2 J CH = 2.9 Hz, CH2); 6.97 (q, 1 J CH = 128.9 Hz, CH3); 17.08 (qt, 1 J CH = 125.8 Hz, 2 J CH = 2.3 Hz, CH3); 21.19 (tc, 1 J CH = 128.8 Hz, 2 J CH = resolution τ 1 / 2 = 12 Hz, CH2); 39.10 (tt, 1 J CH = 139.7 Hz, 2 J CH = 4.4 Hz, CH2); 57.04 (tq, 1 J CH = 141.8 Hz, 2 J CH = 4.5 Hz, CH2); 135.65 (qq, 2 J CH = 7.5 Hz, 3 J CH = 5.7 Hz, C=C); 170.33 (m, C=O).

[0315] 29 Si{ 1 H}-NMR (79.5 MHz, CDCl3, δ, in ppm): -46.0 (s).

[0316] Synthesis of silicone polymers

[0317] Example 1 - MDMMIQ-5030:

[0318] Methyltrimethoxysilane (6.80 g, 50.0 mmol), tetraethyl orthosilicate (4.12 g, 20.0 mmol), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (9.84 g, 30.0 mmol), and propan-2-ol (14.0 g) were placed in a reaction vessel and purged with nitrogen. With rapid stirring, tetraethylammonium hydroxide (10.2 g, 28.0 mmol, 25% in water) was added dropwise to the reaction over 5 minutes. The temperature was controlled <25 °C during the addition. The reaction was stirred at 23 °C under nitrogen for 2 hours. The reaction mixture was poured into a second flask containing rapidly stirred deionized water (14.0 g), 35% hydrochloric acid (3.07 g, 29.4 mmol), and n-propyl acetate (50.0 g). The mixture was stirred at 23 °C for 1 hour and then the aqueous phase was removed. The organic phase was washed with deionized water (30.0 g) and then concentrated in vacuo to approximately 15 cm 3 volume. Propan-2-ol (20 g) was added to the organic phase and the solution was concentrated in vacuo to give Siloxane 1 (18.3 g, 39 wt% in propan-2-ol). GPC (THF, 40 °C): M w = 2,255 g / mol.

[0319] Example 2 - MDMMIQ-5040:

[0320] Methyltrimethoxysilane (6.80 g, 50.0 mmol), tetraethyl orthosilicate (2.08 g, 10.0 mmol), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (13.16 g, 40.0 mmol), and propan-2-ol (14.0 g) were placed in a reaction vessel and purged with nitrogen. With rapid stirring, tetraethylammonium hydroxide (10.9 g, 30.0 mmol, 25% in water) was added dropwise to the reaction over 5 minutes. The temperature was controlled <25 °C during the addition. The reaction was stirred at 23 °C under nitrogen for 2 hours. The reaction mixture was poured into a second flask containing rapidly stirred deionized water (14.0 g), 35% hydrochloric acid (3.29 g, 31.5 mmol), and n-propyl acetate (50.0 g). The mixture was stirred at 23 °C for 1 hour and then the aqueous phase was removed. The organic phase was washed with deionized water (30.0 g) and then concentrated in vacuo to approximately 15 cm 3 volume. Propan-2-ol (20 g) was added to the organic phase and the solution was concentrated in vacuo to give Siloxane 2 (22.7 g, 39 wt% in propan-2-ol). GPC (THF, 40 °C): M w = 1,614 g / mol.

[0321] Example 3 - MDMMIQ-6010:

[0322] Methyltrimethoxysilane (8.16 g, 60.0 mmol), tetraethyl orthosilicate (6.24 g, 30.0 mmol), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (3.29 g, 10.0 mmol) and propan-2-ol (14.0 g) were placed in a reaction vessel and purged with nitrogen. Under rapid stirring, tetramethylammonium hydroxide (5.21 g, 14.3 mmol, 25% in water) was added dropwise to the reaction over 5 minutes. The temperature was controlled <25 °C during the addition. The reaction was stirred at 23 °C under nitrogen for 2 hours. The reaction mixture was poured into a second flask containing rapidly stirred deionized water (14.0 g), 35% hydrochloric acid (1.57 g, 15.0 mmol) and n-propyl acetate (50.0 g). The mixture was stirred at 23 °C for 1 hour and then the aqueous phase was removed. The organic phase was washed with deionized water (30.0 g) and then concentrated in vacuo to about 15 cm 3 volume. Propan-2-ol (20 g) was added to the organic phase and the solution was concentrated in vacuo to give siloxane 3 (15.5 g, 39 wt% in propan-2-ol). GPC (THF, 40 °C): M w = 6,160 g / mol.

[0323] Example 4 - MDMMIQ-8010:

[0324] Methyltrimethoxysilane (10.9 g, 80.0 mmol), tetraethyl orthosilicate (2.08 g, 10.0 mmol), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (3.29 g, 10.0 mmol) and propan-2-ol (14.0 g) were placed in a reaction vessel and purged with nitrogen. Under rapid stirring, tetramethylammonium hydroxide (11.0 g, 30 mmol, 25% in water) was added dropwise to the reaction over 5 minutes. The temperature was controlled <25 °C during the addition. The reaction was stirred at 23 °C under nitrogen for 2 hours. The reaction mixture was poured into a second flask containing rapidly stirred deionized water (14.0 g), 35% hydrochloric acid (3.29 g, 31.5 mmol) and n-propyl acetate (50.0 g). The mixture was stirred at 23 °C for 1 hour and then the aqueous phase was removed. The organic phase was washed with deionized water (30.0 g) and then concentrated in vacuo to about 15 cm 3 volume. Propan-2-ol (20 g) was added to the organic phase and the solution was concentrated in vacuo to give siloxane 4 (14.5 g, 39 wt% in propan-2-ol). GPC (THF, 40 °C): M w= 1,986 g / mol.

[0325] Example 5 - MPDMMIQ-502010:

[0326] Methyltrimethoxysilane (6.80 g, 50.0 mmol), phenyltrimethoxysilane (3.96 g, 20.0 mmol), tetraethyl orthosilicate (4.16 g, 20.0 mmol), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (3.29 g, 10.0 mmol) and propan-2-ol (14.0 g) were placed in a reaction vessel and purged with nitrogen. Under rapid stirring, tetraethylammonium hydroxide (10.9 g, 30.0 mmol, 25% in water) was added dropwise to the reaction over 5 minutes. The temperature was controlled < 25 °C during the addition. The reaction was stirred at 23 °C under nitrogen for 2 hours. The reaction mixture was poured into a second flask containing rapidly stirred deionized water (14.0 g), 35% hydrochloric acid (3.29 g, 31.5 mmol) and n-propyl acetate (50.0 g). The mixture was stirred at 23 °C for 1 hour and then the aqueous phase was removed. The organic phase was washed with deionized water (30.0 g) and then concentrated in vacuo to approximately 15 cm 3 volume. Propan-2-ol (20 g) was added to the organic phase and the solution was concentrated in vacuo to give siloxane 5 (20.5 g, 39 wt% in propan-2-ol). GPC (THF, 40 °C): M w = 2,033 g / mol.

[0327] Example 6 - MPDMMIQ-503010:

[0328] Methyltrimethoxysilane (6.80 g, 50.0 mmol), tetraethyl orthosilicate (2.08 g, 10.0 mmol), phenyltrimethoxysilane (5.95 g, 30.0 mmol), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (3.29 g, 10.0 mmol) and propan-2-ol (14.0 g) were placed in a reaction vessel and purged with nitrogen. Under rapid stirring, tetraethylammonium hydroxide (10.9 g, 30.0 mmol, 25% in water) was added dropwise to the reaction over 5 minutes. The temperature was controlled < 25 °C during the addition. The reaction was stirred at 23 °C under nitrogen for 2 hours. The reaction mixture was poured into a second flask containing rapidly stirred deionized water (14.0 g), 35% hydrochloric acid (3.31 g, 31.5 mmol) and n-propyl acetate (50.0 g). The mixture was stirred at 23 °C for 1 hour and then the aqueous phase was removed. The organic phase was washed with deionized water (30.0 g) and then concentrated in vacuo to approximately 15 cm 3Volume. Propane-2-ol (20 g) was added to the organic phase and the solution was concentrated in vacuo to give siloxane 6 (15.7 g, 39 wt% in propane-2-ol). GPC (THF, 40 °C): M w = 1,899 g / mol.

[0329] Example 7 - MPDMMI-504010:

[0330] Methyltrimethoxysilane (6.80 g, 50.0 mmol), phenyltrimethoxysilane (7.92 g, 40.0 mmol), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (3.29 g, 10.0 mmol) and propane-2-ol (14.0 g) were placed in a reaction vessel and purged with nitrogen. With rapid stirring, tetra-methylammonium hydroxide (10.9 g, 30.0 mmol, 25% in water) was added dropwise to the reaction over 5 minutes. The temperature was controlled < 25 °C during the addition. The reaction was stirred at 23 °C under nitrogen for 2 hours. The reaction mixture was poured into a second flask containing rapidly stirred deionized water (14.0 g), 35% hydrochloric acid (3.29 g, 31.5 mmol) and n-propyl acetate (50.0 g). The mixture was stirred at 23 °C for 1 hour and then the aqueous phase was removed. The organic phase was washed with deionized water (30.0 g) and then concentrated in vacuo to about 15 cm 3 Volume. Propane-2-ol (20 g) was added to the organic phase and the solution was concentrated in vacuo to give siloxane 7 (23.1 g, 39 wt% in propane-2-ol). GPC (THF, 40 °C): M w = 1,626 g / mol.

[0331] Example 8 - MDMMIBe-503020:

[0332] Methyltrimethoxysilane (6.80 g, 50.0 mmol), 1,2-bis(triethoxysilyl)ethane (7.09 g, 20.0 mmol), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (9.84 g, 30.0 mmol) and propan-2-ol (14.0 g) were placed in a reaction vessel and purged with nitrogen. Under rapid stirring, tetraethylammonium hydroxide (7.64 g, 21.0 mmol, 25% in water) was added dropwise to the reaction over 5 minutes. The temperature was controlled <25 °C during the addition. The reaction was stirred at 23 °C under nitrogen for 2 hours. The reaction mixture was poured into a second flask containing rapidly stirred deionized water (14.0 g), 35% hydrochloric acid (2.30 g, 22.1 mmol) and n-propyl acetate (50.0 g). The mixture was stirred at 23 °C for 1 hour and then the aqueous phase was removed. The organic phase was washed with deionized water (30.0 g) and then concentrated in vacuo to about 15 cm 3 volume. Propan-2-ol (20 g) was added to the organic phase and the solution was concentrated in vacuo to give siloxane 8 (29.2 g, 39 wt% in propan-2-ol). GPC (THF, 40 °C): M w = 3,182 g / mol.

[0333] Example 9 - MPQ-5040-HA: (Reference)

[0334] Methyltrimethoxysilane (6.80 g, 50.0 mmol), phenyltrimethoxysilane (7.92 g, 40.0 mmol), tetraethyl orthosilicate (2.08 g, 10.0 mmol) and propan-2-ol (28.0 g) were placed in a reaction vessel and purged with nitrogen. Under rapid stirring, tetraethylammonium hydroxide (11.8 g, 32.4 mmol, 25% in water) was added dropwise to the reaction over 5 minutes. The temperature was controlled <25 °C during the addition. The reaction was stirred at 23 °C under nitrogen for 2 hours. The reaction mixture was poured into a second flask containing rapidly stirred deionized water (34.0 g), 35% hydrochloric acid (3.54 g, 34.0 mmol) and n-propyl acetate (34.0 g). The mixture was stirred at 23 °C for 1 hour and then the aqueous phase was removed. The organic phase was washed with deionized water (30.0 g) and then concentrated in vacuo to about 15 cm 3 volume. Propan-2-ol (20 g) was added to the organic phase and the solution was concentrated in vacuo to give siloxane 9 (23.0 g, 39 wt% in propan-2-ol). GPC (THF, 40 °C): M w = 1,322 g / mol.

[0335] Example 10 - MPQ-5040-LA: (Reference)

[0336] Methyltrimethoxysilane (6.80 g, 50.0 mmol), phenyltrimethoxysilane (7.92 g, 40.0 mmol), tetraethyl orthosilicate (2.08 g, 10.0 mmol) and propan - 2 - ol (28.0 g) were placed in a reaction vessel and purged with nitrogen. Under rapid stirring, tetra - methylammonium hydroxide (8.22 g, 22.6 mmol, 25% in water) was added dropwise to the reaction over 5 minutes. The temperature was controlled <25 °C during the addition. The reaction was stirred under nitrogen at 23 °C for 2 hours. The reaction mixture was poured into a second flask containing rapidly stirred deionized water (34.0 g), 35% hydrochloric acid (2.48 g, 23.7 mmol) and n - propyl acetate (34.0 g). The mixture was stirred at 23 °C for 1 hour and then the aqueous phase was removed. The organic phase was washed with deionized water (30.0 g) and then concentrated in vacuo to about 15 cm 3 volume. Propan - 2 - ol (20 g) was added to the organic phase and the solution was concentrated in vacuo to give siloxane 10 (23.0 g, 39 wt% in propan - 2 - ol). GPC (THF, 40 °C): M w = 2,262 g / mol.

[0337] Photopatterning and properties

[0338] Photopatterning

[0339] The substrates (glass or Si wafers) were each washed in acetone and isopropanol for 10 minutes according to the standard process of continuous ultrasonic treatment. Each positive photoresist formulation (20 - 40% total solids content) was applied onto 4 - inch silicon wafers or glass substrates by spin - coating (1,000 to 2,000 rpm) to obtain a uniform film with a target thickness of 1 to 3 μm. The obtained film was pre - baked at 100 °C for 90 seconds to evaporate the solvent (process step (1)). The dried coating film was exposed to light in the shape of line - and - space and hole patterns (4 - μm line, 12 - μm space) using 100 to 500 mJ / cm 2 by broadband illumination to suit ghi - line (wavelength: 365 to 436 nm) photoresist processing (process step (2a)). Subsequently, it was subjected to puddle development with a 2.38% aqueous TMAH solution for 120 seconds and further rinsed with pure water for 60 seconds (process step (2b)). After drying, the cone angle of the developed pattern was measured using a scanning electron microscope (SEM). Additionally, the developed pattern was subjected to exposure with 1,000 mJ / cm 2 using either a g + h + i line mask aligner or 100 mJ / cm 2Expose the whole piece at 230 nm with a UV lamp, and then heat it at 250 °C for 30 minutes in air or nitrogen to cure. Observe the cured pattern using a scanning electron microscope (SEM) to measure its taper angle. At the same time, observe the line width of the pattern using SEM after development and additionally after a post-baking step to measure the line width increase ratio.

[0340] Adhesion on glass

[0341] Cut the cured pattern (see photo patterning) together with the substrate into smaller pieces, and bond the plastic nails and the cured film via an epoxy resin layer. Next, pull the nails apart, and measure the load at peeling using a thin film adhesion strength measuring machine (i.e., Romulus manufactured by Quad Group).

[0342] Photoresist formulation using a photoacid generator (PAG)

[0343] Examples 101 to 106 and Reference 100: Prepare a positive photoresist formulation containing a photoacid generator (PAG) according to the composition shown in Table 1. The amounts given in the table are reference parts by mass and are designated as percentages (phr).

[0344] Photoactive agent: 4,4'-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol modified with 2.0 moles of naphthoquinone diazide sulfonic acid.

[0345] Photoacid generator: 1,8-naphthalimide trifluoromethanesulfonate (NAI-105, Midori Kagaku Co., Ltd.).

[0346] Surfactant: Diphenyldimethylsiloxane (KF-53, Shin-Etsu Chemical Co., Ltd.).

[0347]

[0348]

[0349] Table 1: Composition and evaluation of Examples 101 to 106 and Reference 100. NM: Not measured; ND: Not defined.

[0350] As can be seen from the experimental results in Table 1, the flow behavior is inhibited by increasing the amount of the first repeating unit and / or the third repeating unit in the siloxane polymer (see Example 101, which includes Siloxane 1 (MDMMIQ-5030) prepared using 20 parts of tetraethyl orthosilicate (TEOS); Example 104, which includes Siloxane 7 (MPDMMI 504010) not prepared using tetraethyl orthosilicate (TEOS); and Reference 100 (MPQ-5040-HA / LA)). The crosslinking of TEOS (the third repeating unit) at a relatively low temperature (<120 °C) enables the crosslinking of the photoresist formulation to occur faster than the flow. However, increasing the amount of TEOS results in a more rigid and more brittle film, which reduces the cracking threshold of the photoresist coating after curing. The repeating unit containing DMMI (the first repeating unit) can be crosslinked by UV light in the full wafer exposure process step, so that the obtained pattern is structurally fixed.

[0351] Figure 2a Photoresist formulation of Reference 100 (MPQ-5040-HA / LA standard formulation) shown after development and after post-baking.

[0352] Figure 2b Photoresist formulation of Example 101 shown after development and after post-baking.

[0353] The novel DMMI-containing siloxane polymer in the photoresist formulation of Example 101 provides excellent patterns, while the MPQ siloxane polymer in the photoresist formulation of Reference 100 is deliquescent.

[0354] Furthermore, it was found that the photoresist formulation according to the present invention shows improved adhesion on the substrate (see Example 104 (34 mPas) containing Siloxane 7 (MPDMMI-504010); and Reference 100 (MPQ-5040-HA / LA) (21 mPas)).

[0355] Improved photosensitivity

[0356] Examples 107 and Reference 101: Positive photoresist formulations were prepared according to the compositions shown in Table 2. The amounts given in the table refer to parts by mass and are designated as percentages (phr).

[0357] Photoactive agent: 4,4'-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol modified with 2.0 moles of naphthoquinone diazide sulfonic acid.

[0358] Photoacid generator: 1,8-naphthalimide ester of trifluoromethanesulfonic acid (NAI-105, Midori Kagaku Co., Ltd.).

[0359] Surfactant: Diphenyldimethylsiloxane (KF-53, Shin-Etsu Chemical Co., Ltd.).

[0360]

[0361] Table 2: Composition and evaluation of Example 107 and Reference 101.

[0362] In addition, when compared to standard MPQ silicone polymers, the novel DMMI-containing silicone polymers offer higher photosensitivity (see Example 102 (10 mJ / cm 2 ) containing silicone 5 (MPDMMIQ-502010); and Reference 101 (MPQ-5040-HA / LA) (133 mJ / cm 2 ))).

[0363] Photosensitivity or light power time is extremely important as it improves the exposure cycle time. Formulations with higher photosensitivity require shorter exposure times and are particularly suitable for thick film applications. It has a positive impact on the so-called cone angle and pattern shape. If the development speed between the exposed and unexposed areas is high, a more vertical pattern can be obtained, while a slow development speed provides a reduced film thickness and a tapered pattern. The positive photoresist formulations of the present invention offer various possibilities to change or modify the shape and contrast of the obtained light pattern.

[0364] Photoresist formulations that do not utilize a photoacid generator (PAG)

[0365] Examples 201 to 205 and Reference 200: Positive photoresist formulations without a photoacid generator were prepared according to the compositions shown in Table 3. The amounts given in the table are reference parts by mass and are designated as percentages (phr).

[0366] Photoactive agent: 4,4'-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol modified with 2.0 moles of naphthoquinone diazide sulfonic acid.

[0367] Surfactant: Diphenyldimethylsiloxane (KF-53, Shin-Etsu Chemical Co., Ltd.).

[0368]

[0369]

[0370] Table 3: Composition and evaluation of Examples 201 to 205 and Reference 200.

[0371] The experimental results in Table 3 show that the positive photoresist formulation according to the present invention exhibits excellent performance even without adding a photoacid generator (PAG). The photoresist formulation of Example 204 is highly reactive due to the presence of repeating units (third repeating units) derived from 1,2-bis(triethoxysilyl)ethane in the siloxane polymer.

Claims

1. A positive photoresist formulation, comprising: (a) a siloxane polymer comprising a first repeating unit and a second repeating unit; and (b) a photoactive dissolution regulator; wherein the first repeating unit contains at least one maleimide group; and the second repeating unit does not contain a maleimide group.

2. The positive photoresist formulation according to claim 1, wherein the first repeating unit is derived from a first siloxane monomer represented by the following formula (1): wherein: L 1 、 L 2 and L 3 are the same as or different from each other and are each independently selected from R, OR, and halogen, where at least one of L 1 、 L 2 and L 3 is OR or halogen; R is selected from the group consisting of H, a straight-chain alkyl group having 1 to 30 carbon atoms, a branched-chain alkyl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and an aryl group having 6 to 20 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 -, or -C≡C-, and wherein one or more H atoms are optionally replaced by F; R 1 and R 2 are the same as or different from each other and each independently selected from H, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, wherein one or more H atoms are optionally replaced by F, or R 1 and R 2 together form a monocyclic or polycyclic organic ring system, wherein one or more H atoms are optionally replaced by F; Z represents a straight-chain alkylene having 1 to 20 carbon atoms, a branched-chain alkylene having 3 to 20 carbon atoms, or a cyclic alkylene having 3 to 20 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 -, or -C≡C-, and wherein one or more H atoms are optionally replaced by F; Y 1 and Y 2 identical to or different from each other and each independently selected from H, F, Cl, and CN; R 0 and R 00 are the same as or different from each other and each independently selected from H, a straight-chain alkyl group having 1 to 20 carbon atoms, and a branched-chain alkyl group having 3 to 20 carbon atoms, and these groups are optionally fluorinated.

3. The positive photoresist formulation according to claim 2, wherein one of the conditions (1) or (2) applies: (1)L 1 = L 2 = L 3 = OR; or (2)L 1 = L 2 = R, and L 3 = Cl.

4. The positive photoresist formulation according to claim 2 or 3, wherein R 1 and R 2 are the same as or different from each other and are each independently selected from H, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 14 carbon atoms, wherein one or more H atoms are optionally replaced by F, or R 1 and R 2 together form a monocyclic or polycyclic aliphatic ring system, a monocyclic or polycyclic aromatic ring system, or a polycyclic aliphatic and aromatic ring system, wherein one or more H atoms are optionally replaced by F.

5. The positive photoresist formulation according to any one of claims 1 to 3, wherein the second repeating unit is derived from a second siloxane monomer represented by one of the following structures S1 or S2: wherein: L 11 、L 12 and L 13 are the same as or different from each other and each independently selected from OR' and halogen; R’ is selected from the group consisting of a straight-chain alkyl group having 1 to 30 carbon atoms, a branched-chain alkyl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and an aryl group having 6 to 20 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 -, or -C≡C-, and wherein one or more H atoms are optionally replaced by F; R 11 and R 12 are the same as or different from each other and each independently selected from the group consisting of H, a straight-chain alkyl group having 1 to 30 carbon atoms, a branched-chain alkyl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and these groups optionally contain one or more functional groups selected from -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CR 0 =CR 00 2-, -CY 1 =CY 2 -, and -C≡C-, and one or more H atoms are optionally replaced by F; and R 0 、R 00 、Y 1 and Y 2 as defined in claim 2.

6. The positive photoresist formulation according to claim 5, wherein the second siloxane monomer is represented by the following structure S1: wherein: L 11 、L 12 and L 13 are the same as or different from each other and each independently selected from OR'; R’ is selected from the group consisting of a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 14 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 -, or -C≡C-, and wherein one or more H atoms are optionally replaced by F, R 11 selected from the group consisting of H, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 14 carbon atoms, these groups optionally containing one or more functional groups selected from -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CR 0 =CR 00 2-, -CY 1 =CY 2 -, and -C≡C-, and one or more H atoms are optionally replaced by F; and R 0 、R 00 、Y 1 and Y 2 as defined in claim 2.

7. The positive photoresist formulation according to claim 6, wherein R’ is selected from the group consisting of a straight-chain alkyl group having 1 to 12 carbon atoms, a branched-chain alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 14 carbon atoms; and R 11 selected from the group consisting of -CH3, -CF3, -C2H5, -C2F5, -C3H7, -C3F7, -C4H9, -C4F9, -C5H 11 , -C5H4F7, -C6H 13 , -C6H4F9, -C7H 15 , -C7H4F 11 , -C8H 17 , -C8H4F 13 , -CH=CH2, -C(CH3)=CH2, -C3H6-O-C(=O)-CH=CH2, -C3H6-O-C(=O)-C(CH3)=CH2, -C6H5 and -C6F5 8. The positive photoresist formulation according to any one of claims 1 to 3, wherein the siloxane polymer further comprises a third repeating unit, wherein the third repeating unit does not contain a maleimide group.

9. The positive photoresist formulation according to claim 8, wherein the third repeating unit is derived from a third siloxane monomer represented by one of the following structures T1 or T2: wherein: L 21 、L 22 、L 23 and L 24 are the same as or different from each other and are each independently selected from OR” and halogen; R” is selected from the group consisting of straight-chain alkyl groups having 1 to 30 carbon atoms, branched-chain alkyl groups having 3 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms, and aryl groups having 6 to 20 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 -, or -C≡C-, and wherein one or more H atoms are optionally replaced by F; Z is absent or represents a straight-chain alkylene group having 1 to 20 carbon atoms, a branched-chain alkylene group having 3 to 20 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 -, - or -C≡C- substitution, and wherein one or more H atoms are optionally replaced by F; and R 0 、R 00 、Y 1 and Y 2 as defined in claim 2.

10. The positive photoresist formulation according to claim 9, wherein the third siloxane monomer is represented by the following structure T1: wherein: L 21 , L 22 , L 23 and L 24 are the same as or different from each other and are independently selected from OR"; R” is selected from the group consisting of straight-chain alkyl groups having 1 to 20 carbon atoms, branched-chain alkyl groups having 3 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, and aryl groups having 6 to 14 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 -, or -C≡C-, and wherein one or more H atoms are optionally replaced by F; and R 0 , R 00 , Y 1 and Y 2 As defined in claim 2.

11. The positive photoresist formulation according to claim 9, wherein the third siloxane monomer is represented by the following structure T2: where L 21 、L 22 and L 23 are the same as or different from each other and are independently selected from OR"; R” is selected from the group consisting of a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 14 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 -, or -C≡C-, and wherein one or more H atoms are optionally replaced by F; Z is absent or represents a straight-chain alkylene having 1 to 12 carbon atoms, a branched alkylene having 3 to 12 carbon atoms, or a cyclic alkylene having 3 to 12 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 -, - or -C≡C-; and wherein one or more H atoms are optionally replaced by F; and R 0 , R 00 , Y 1 and Y 2 As defined in claim 2.

12. The positive photoresist formulation according to any one of claims 1 to 3, wherein the siloxane polymer further comprises one or more additional repeating units, wherein the one or more additional repeating units do not contain a maleimide group and are derived from one or more additional siloxane monomers represented by the following structure F1: wherein: L 31 、L 32 and L 33 are the same as or different from each other and each independently selected from OR''' and halogen; R”’ is selected from the group consisting of straight-chain alkyl groups having 1 to 30 carbon atoms, branched-chain alkyl groups having 3 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms, and aryl groups having 6 to 20 carbon atoms, wherein one or more non-adjacent and non-terminal CH2 groups are optionally replaced by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 -, or -C≡C-, and wherein one or more H atoms are optionally replaced by F; R 31 selected from the group consisting of H, straight-chain alkyl groups having 1 to 30 carbon atoms, branched-chain alkyl groups having 3 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms, and aryl groups having 6 to 20 carbon atoms, these groups optionally containing one or more functional groups selected from -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CR 0 =CR 00 2-, -CY 1 =CY 2 -, and -C≡C-, and one or more H atoms are optionally replaced by F; and R 0 , R 00 , Y 1 and Y 2 As defined in claim 2.

13. The positive photoresist formulation according to any one of claims 1 to 3, wherein the mole fraction of the first repeating unit in the siloxane polymer is in the range of 1 to 90%, based on the total amount of repeating units in the siloxane polymer.

14. The positive photoresist formulation according to any one of claims 1 to 3, wherein the mole fraction of the second repeating unit in the siloxane polymer is in the range of 10 to 90%, based on the total amount of repeating units in the siloxane polymer.

15. The positive photoresist formulation according to claim 8, wherein the mole fraction of the third repeating unit in the siloxane polymer is in the range of 0 to 50%, based on the total amount of repeating units in the siloxane polymer.

16. A positive photoresist formulation according to any one of claims 1 to 3, wherein the photoactive dissolution regulator is selected from diazonaphthoquinone (DNQ) or its derivatives.

17. A positive photoresist formulation according to any one of claims 1 to 3, which comprises one or more additional silicone polymers, wherein the additional silicone polymers do not contain maleimide groups.

18. A method of manufacturing a microelectronic structure, which comprises the following steps: (1) applying a positive photoresist formulation according to any one of claims 1 to 17 to the surface of a substrate; (2) subjecting the positive photoresist formulation applied in step (1) to photolithography to obtain a photopatterned structure; and (3) curing the photopatterned structure obtained in step (2) to obtain a cured photopatterned dielectric material on the surface of the substrate.

19. An electronic device, which comprises a microelectronic structure obtainable by the manufacturing method according to claim 18.

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