Semiconductor device, terminal, electronic device, and substrate surface patterning method

Abstract

The application provides a semiconductor device, comprising: a substrate; a modification layer on a surface of the substrate, the modification layer being locally exposed, the modification layer comprising an exposed part and an unexposed part, the unexposed part having a group A, and the exposed part having a group B formed by transformation of the group A; and a patterned characteristic particle layer on a surface of the modification layer away from the substrate and locally covering the unexposed part, the characteristic particle layer having a group C which has a bonding reaction with the group A and does not react with the group B, and the characteristic particle layer being combined with the unexposed part through the bonding reaction of the group A and the group C. The application also provides a terminal and an electronic device using the semiconductor device and a substrate surface patterning method. The substrate surface patterning method of the application uses simple materials and can realize a high-resolution pattern with low edge roughness.

Description

TECHNICAL FIELD

[0001] The present application relates to a semiconductor device, a terminal and an electronic device using the semiconductor device, and a substrate surface patterning method for forming the semiconductor device. BACKGROUND

[0002] Patterning process is a key technology to promote the development of integrated circuit manufacturing related industry. The development of patterning process makes it possible to realize electronic devices with lighter, faster response speed, and lower manufacturing cost. The patterning process generally includes the following steps: a) applying a patterning material on the surface of a substrate to form a uniform modification layer with a certain thickness; b) through the reflection / transmission effect of a mask plate with a pattern, the light with pattern information is finally irradiated on the modification layer of the patterning material through a reflection or transmission light path system, so that the modification layer of the patterning material forms a structure with irradiated coating area and non-irradiated coating area; c) using a specific solvent / solution to selectively dissolve the irradiated coating area or non-irradiated coating area of the modification layer of the patterning material; d) the remaining part of the modification layer of the patterning material can be resistant to etching and can selectively protect the substrate from etching or slow etching, and then a pattern is formed on the substrate, such as a silicon wafer, which is consistent with the pattern in the selectively exposed mask plate.

[0003] The patterning process involves a variety of materials and complex process steps. As the wavelength of the light source used in the patterning process gradually decreases, it is possible to further realize the fine structure in the integrated circuit. However, each generation of wavelength evolution involves the evolution of the whole series of process steps, materials, and equipment. The most advanced process in current integrated circuit manufacturing uses 13.5 nm wavelength as the exposure light source. Under this wavelength condition, limited by the sensitivity of the patterning material, the patterning quality and resolution limit that can be achieved by the current patterning material system is 10-15 nm, which cannot meet the advanced demand for finer structures in the industry. SUMMARY

[0004] The first aspect of the embodiment of the present application provides a semiconductor device, comprising:

[0005] a substrate;

[0006] a modification layer on a surface of the substrate, the modification layer being locally exposed, the modification layer comprising an exposed part and a non-exposed part, the non-exposed part of the modification layer having a group A, and the exposed part of the modification layer having a group B formed by the exposure of the group A; and

[0007] a patterned layer of characteristic particles on the surface of the modification layer remote from the substrate and covering the unexposed portions of the modification layer, the layer of characteristic particles having groups C that bond with the groups A without reacting with the groups B, the layer of characteristic particles being bound to the unexposed portions of the modification layer by the bonding of the groups A and the groups C.

[0008] The semiconductor device of the present application is selectively exposed through the modification layer, the groups A of which are chemically changed, and a functional layer of characteristic particles is used to bond with the groups A of the unexposed modification layer, so that the layer of characteristic particles is firmly bound to the unexposed portions of the modification layer, thereby forming a patterned layer of characteristic particles that is functional (including etch resistance, special dielectricity, etc.), has low exposure energy requirement, high resolution, and low pattern edge roughness.

[0009] In the embodiments of the present application, the groups A are at least one of the following end groups: azido, alkenyl, aldehyde, thiol, substituted or unsubstituted amino, alkynyl, ester, carboxylic acid, halogen, hydroxyl, epoxy, cyanate, thiocyanate, isothiocyanate, a group that serves as a polydentate ligand,

[0010] In the embodiments of the present application, the material of the unexposed portions of the modification layer has the general chemical formula: A—C a H b X c —E, wherein X is one or more of the third, fourth, fifth, sixth, and seventh main groups of elements, 45≧a≧1, 90≧b≧1, 90≧c≧0; the group E is a molecular group containing an end group, which is at least one of the following: amino-type end group, thiol-type end group, end group that can be hydrolyzed into silanol or hydroxyl.

[0011] In the embodiments of the present application, when the groups A are azido, the groups C are alkynyl or

[0012] When the groups A are alkenyl, the groups C are thiol;

[0013] When the groups A are aldehyde, the groups C are H2N—O—;

[0014] When the groups A are the groups C are or alkenyl connected with an unsaturated group;

[0015] When the groups A are epoxy, the groups C are amino.

[0016] In the embodiments of the present application, when the groups A are azido, the groups B are amino;

[0017] when the group A is aldehyde group, the group B is hydroxyl group;

[0018] when the group A is aldehyde group, the group B is hydroxyl group;

[0019] when the group A is aldehyde group, the group B is hydroxyl group;

[0020] when the group A is aldehyde group, the group B is hydroxyl group;

[0021] when the group A is aldehyde group, the group B is hydroxyl group;

[0022] when the group A is aldehyde group, the group B is hydroxyl group;

[0023] when the group A is aldehyde group, the group B is hydroxyl group;

[0024] when the group A is aldehyde group, the group B is hydroxyl group;

[0025] when the group A is aldehyde group, the group B is hydroxyl group;

[0026] when the group A is aldehyde group, the group B is hydroxyl group;

[0027] when the group A is aldehyde group, the group B is hydroxyl group;

[0028] when the group A is aldehyde group, the group B is hydroxyl group;

[0029] when the group A is aldehyde group, the group B is hydroxyl group;

[0030] when the group A is aldehyde group, the group B is hydroxyl group; when the group A is aldehyde group, the group B is hydroxyl group;

[0031] when the group A is aldehyde group, the group B is hydroxyl group; when the group A is aldehyde group, the group B is hydroxyl group;

[0032] when the group A is aldehyde group, the group B is hydroxyl group; when the group A is aldehyde group, the group B is hydroxyl group;

[0033] when the group A is aldehyde group, the group B is hydroxyl group; when the group A is aldehyde group, the group B is hydroxyl group.

[0034] In the embodiments of the present application, the substrate is a silicon wafer, a quartz wafer or a metal sheet, or the substrate is a substrate obtained by adding other materials to a silicon wafer, a quartz wafer or a metal sheet through surface modification.

[0035] In the embodiments of the present application, the characteristic particle layer is a dielectric material layer.

[0036] In the embodiment, the characteristic particle layer contains the characteristic particles having the group C, and the molecular size of the characteristic particles is 0.2-20 nm.

[0037] The second aspect of the embodiment provides a terminal, which comprises a shell and a semiconductor device accommodated in the shell, and the semiconductor device comprises the semiconductor device described above.

[0038] The third aspect of the embodiment provides a substrate surface patterning method, which comprises:

[0039] providing a substrate;

[0040] forming a modification layer on a surface of the substrate, the modification layer having a group A, and the group A is exposed on the surface of the substrate;

[0041] performing local exposure on the modification layer, so that the group A of the exposed part of the modification layer is changed to form a group B;

[0042] forming a characteristic particle layer on the modification layer, and the characteristic particles in the characteristic particle layer have a group C which can bond with the group A and does not react with the group B; and

[0043] using a developing solution to remove the part of the characteristic particle layer which does not bond with the modification layer.

[0044] The substrate surface patterning method of the embodiment uses simple materials, can realize high resolution, and the patterned characteristic particle layer has low pattern edge roughness.

[0045] In the embodiment, the characteristic particle layer contains an etch-resistant material or a dielectric material.

[0046] In the embodiment, the group A is at least one of the following end groups: azido, alkenyl, aldehyde, thiol, substituted or unsubstituted amino, alkynyl, ester, carboxylic acid group, halogen, hydroxyl, epoxy, cyanate, thiocyanate, isothiocyanate, a group used as a polydentate ligand,

[0047] In the embodiment, the material of the modification layer before the local exposure has a chemical formula: A-C a H b X c—E, wherein X is one or more of the third, fourth, fifth, sixth and seventh main groups, wherein 45 > a > 1, 90 > b > 1, 90 > c > 0; the group E is a molecular group containing a terminal group, which is at least one of the following: an amino type terminal group, a mercapto type terminal group, a terminal group hydrolysable to a silicon hydroxyl group or a hydroxyl group.

[0048] In the embodiment of the present application, the characteristic particle layer contains the characteristic particles having the group C, and the molecular size of the characteristic particles is 0.2-20 nm.

[0049] In the embodiment of the present application, the characteristic particles are etch-resistant molecules; and the substrate surface patterning method further comprises etching the area of the substrate not covered by the characteristic particle layer to transfer the pattern to the substrate.

[0050] In the embodiment of the present application, the step of locally exposing the modification layer to soft X-ray uses any single wavelength or mixed wavelength ray in the wavelength range of 1-15 nm; or uses an electron beam.

[0051] In the embodiment of the present application, the step of locally exposing the modification layer to soft X-ray uses a mask plate, and the soft X-ray with pattern information passes through the mask plate to locally expose the modification layer.

[0052] In the embodiment of the present application, the substrate surface patterning method further comprises using heating baking or ultraviolet or infrared irradiation to promote the bonding reaction between the group C of the characteristic particles in the characteristic particle layer and the group A of the modification layer.

[0053] In the embodiment of the present application, the developing solution is a tetramethylammonium hydroxide solution, a ketone organic solvent, an alcohol organic solvent, an ether organic solvent, an ester organic solvent, a lactone organic solvent.

[0054] The substrate surface patterning method of the present application uses a light source with a wavelength of 1-15 nm or an electron beam to selectively damage the functional terminal group A of the modification layer on the substrate, and uses the functional characteristic nanoparticles to bond with the modification layer not exposed to light, to form a pattern with the characteristics of low exposure energy requirement, high resolution, low pattern edge roughness, and functional properties (including etch resistance, special dielectricity, etc.).

[0055] The fourth aspect of the embodiment of the present application provides an electronic device including an integrated circuit, and the integrated circuit includes the semiconductor device described above.

[0056] The semiconductor device of the present application has a patterned characteristic particle layer with the characteristics of low exposure energy requirement, high resolution, and low edge roughness; thereby facilitating the processing of the integrated circuit of the electronic device using the semiconductor device. BRIEF DESCRIPTION OF DRAWINGS

[0057] Figure 1 is a schematic diagram of a cross-sectional structure of a semiconductor device according to an embodiment of the present application.

[0058] Figure 2 is a diagram of several chemical structures of a characteristic particle contained in a characteristic particle layer.

[0059] Figure 3 is a flowchart of a substrate surface patterning method according to an embodiment of the present application.

[0060] Figure 4 is a schematic diagram of steps S1-S3 in a substrate surface patterning method.

[0061] Figure 5 is a schematic diagram of steps S4-S6 in a substrate surface patterning method.

[0062] Explanation of Main Elements

[0063] Semiconductor device 100

[0064] Substrate 10

[0065] Modification layer 30

[0066] Exposed portion 31

[0067] Unexposed portion 33

[0068] Characteristic particle layer 50

[0069] Mask plate 60

[0070] Through hole 61 DETAILED DESCRIPTION

[0071] The embodiments of the present application will be described below in conjunction with the accompanying drawings.

[0072] An electronic device (not shown in the drawings) includes an integrated circuit (not shown in the drawings) including a semiconductor device. Existing semiconductor devices generally include some patterned functional layers (e.g., dielectric material layers). The patterning quality and resolution limit of current patterning material systems are 10-15 nm, which cannot meet the industry's demand for more advanced and smaller structures. Therefore, the present application provides a semiconductor device having a patterned layer with higher resolution.

[0073] Please refer to Figure 1The semiconductor device 100 of the embodiment of the present application comprises a substrate 10, a modification layer 30 and a characteristic particle layer 50 which are sequentially stacked from bottom to top. The modification layer 30 covers a surface of the substrate 10; the characteristic particle layer 50 covers a surface of the modification layer 30 away from the substrate 10. The characteristic particle layer 50 partially covers the modification layer 30. The characteristic particle layer 50 is patterned, thus it partially covers the modification layer 30.

[0074] The resolution of the patterned characteristic particle layer 50 is high, between 0.2 and 100 nm, i.e. the resolution can be between 0.2 and 10 nm, and the edge roughness is between 2% and 30% of the pattern resolution.

[0075] The modification layer 30 can be a monomolecular layer or a multilayer film, which is an organic material layer. The modification layer 30 is formed by local exposure, and before exposure, the modification layer 30 has groups A capable of undergoing a bonding reaction. The modification layer 30 is locally exposed by high-energy rays or electron beams, comprising exposed portions 31 and unexposed portions 33. The unexposed portions 33 of the modification layer 30 have groups A; the exposed portions 31 of the modification layer 30 do not have groups A, but have groups B formed by the transformation of the groups A upon exposure to high-energy rays or electron beams. The characteristic particle layer 50 only covers the unexposed portions 33 of the modification layer 30, and does not cover the exposed portions 31 of the modification layer 30. The characteristic particles contained in the characteristic particle layer 50 have groups C, which undergo a bonding reaction with the groups A but do not react with the groups B. Thus, when a material of characteristic particles is laid on a surface of the modification layer 30 to completely cover the surface, the characteristic particles in the exposed portions 31 do not undergo a chemical reaction, and thus can be easily removed. The groups C of the remaining characteristic particles undergo a chemical bonding reaction with the groups A of the unexposed portions 33 to form a characteristic particle layer 50 with a specific pattern, and the characteristic particle layer 50 is firmly combined with the unexposed portions 33.

[0076] The substrate 10 can be a silicon wafer, a quartz sheet or a metal sheet, and can also be a substrate obtained by adding other materials to the surface of the silicon wafer, the quartz sheet or the metal sheet. In the embodiment, the characteristic particle layer 50 is a dielectric material layer.

[0077] The group A is an end group exposed on the surface of the modification layer 30, which can be at least one of the following end groups, including: azido group (—N3), alkenyl group (—CH=CH2), aldehyde group (—CHO), epoxy group (—CH(O)CH—), mercapto group (—SH), substituted or unsubstituted amino group (—NH2), alkynyl group (CH≡C—), ester group (—COOR), carboxylic acid group (—COOH), halogen group, hydroxyl group (—OH), cyanate group (—OC≡N), thiocyanate group, isothiocyanate group, groups used as polydentate ligands (such as crown ether, cyclodextrin, EDTA group, etc.), and the like,

[0078] In one embodiment, the chemical formula of the unexposed part 33 of the modification layer 30 is: A—C a H b X c —E, wherein X is one or several of the third, fourth, fifth, sixth, and seventh main group elements, wherein 45≧a≧1, 90≧b≧1, 90≧c≧0; the group E is a molecular group containing the following end groups, including but not limited to: amino-type end groups (such as —NH2, —NH), mercapto-type end groups (—SH), hydrolyzable to silanol-type end groups (such as —Si(OR)2, —Si(OR)3, —SiCl2, —SiCl3) or hydroxyl-type end groups (—OH). The siloxane-type end group of the group E can react with the substrate 20, fix the molecule on the substrate 10, and expose the group A which can undergo bonding reaction on the surface of the substrate.

[0079] The high-energy rays used to expose the modification layer 30 are any single-wavelength rays or mixed-wavelength rays of soft X-rays with a wavelength in the range of 1-15 nm; or electron beams are used.

[0080] The following are several groups B formed by the exposure of groups A, as follows:

[0081] When the group A is an azido group, the group B is an amino group;

[0082] When the group A is an alkenyl group, the group B is an alkyl group;

[0083] When the group A is an aldehyde group, the group B is a hydroxyl group;

[0084] When the group A is an epoxy group, the group B is a hydroxyl group;

[0085] When the group A is a mercapto group, the group B is an alkenyl group;

[0086] When the group A is a substituted or unsubstituted amino group, the group B is an alkenyl group;

[0087] when the group A is an ester group, the group B is a hydroxyl group;

[0088] when the group A is an ester group, the group B is a hydroxyl group;

[0089] when the group A is a carboxylic acid group, the group B is a hydroxyl group;

[0090] when the group A is a halogen group, the group B is an alkenyl group;

[0091] when the group A is a hydroxyl group, the group B is an alkenyl group;

[0092] when the group A is a cyanate group, the group B is a hydroxyl group;

[0093] when the group A is a thiocyanate group, the group B is a mercapto group;

[0094] when the group A is an isothiocyanate group, the group B is an amino group;

[0095] when the group A is an isothiocyanate group, the group B is an amino group; the group B is a succinimidyl group;

[0096] when the group A is an isothiocyanate group, the group B is an amino group; the group B is a succinimidyl group;

[0097] when the group A is an isothiocyanate group, the group B is an amino group; the group B is a succinimidyl group;

[0098] when the group A is an isothiocyanate group, the group B is an amino group; the group B is a succinimidyl group.

[0099] Several groups A, groups C with which the groups A can be bonded, groups B which are formed from the groups A by exposure, and chemical bonds D between the groups A and the groups C are listed below, as shown in Table 1.

[0100] Table 1

[0101]

[0102]

[0103] Taking the azido group (-N3) as an example, the group is changed to a group B (amino group (-NH2)) and nitrogen gas (N2) is released by soft X-ray irradiation. The amino group does not further bond with the group C (alkynyl group) of the characteristic particle under the original conditions. The group A at the unexposed position bonds with the group C (alkynyl group) of the characteristic particle, thereby fixing the characteristic particle on the surface of the substrate.

[0104] The group C is not limited to the groups listed in Table 1, as long as it can chemically pair with group A and cannot chemically pair with group B that is converted by high-energy radiation exposure. For example, when the group A is The group C can also be an unsaturated group (such as a carbonyl group, a sulfone group, etc.) connected to an alkenyl group.

[0105] The characteristic particle layer 50 contains characteristic particles having the group C, which can be etch-resistant particles, special dielectric performance particles, or other special performance particles, including but not limited to etch-resistant organic molecules, inorganic molecules, organic silicon cages, organic or inorganic metal cage molecules, rod-shaped structure molecules, etc., and other shaped nanoparticles. For example: silicon oxide nanoparticles wrapped with polymerizable groups, particle size 0.2-20 nm; silicon cage molecules with polymerizable groups, molecular size 0.2-20 nm; metal nanoparticles wrapped with polymerizable organic groups, size 0.2-20 nm; metal organic cluster molecules containing polymerizable groups, size 0.2-20 nm; C60 carbon cage macromolecules modified with polymerizable groups, size 0.2-20 nm; and other spherical, rod-shaped, core-shell, etc. three-dimensional structure macromolecules or nanoparticles with molecular size 0.2-20 nm. Figure 2 Several structures of the characteristic particles contained in the characteristic particle layer 50 are shown, (a) siloxane three-dimensional structure, (b) carbon-based three-dimensional structure macromolecule, (c) metal framework-containing macromolecule, and (d) characteristic nanoparticle.

[0106] The modification layer can be a monolayer or a multilayer, and its thickness can be 0.1 nm-100 nm. The characteristic particle layer 50 can be a monolayer or a multilayer, and its thickness can be 0.2-200 nm.

[0107] The embodiment of the present application also provides a terminal (not shown in the figure), which comprises a shell (not shown in the figure) and a semiconductor device accommodated in the shell, and the semiconductor device comprises the semiconductor device 100 described above.

[0108] Please refer to Figure 3 The embodiment of the present application provides a substrate surface patterning method, which comprises:

[0109] Step S1: providing a substrate;

[0110] Step S2: forming a modification layer on a surface of the substrate, the modification layer having a group A, and the group A being exposed on the surface of the substrate;

[0111] Step S3: locally exposing the modification layer, so that the group A of the exposed part of the modification layer is changed to form a group B;

[0112] Step S4: A characteristic particle layer is formed on the modified layer, wherein the characteristic particles in the characteristic particle layer have a group C that can bond and react with group A but not with group B; and

[0113] Step S5: Use a developing solution to remove the portion of the characteristic particle layer that has not bonded to the modified layer.

[0114] like Figure 4 The substrate 10 shown can be a silicon wafer, a quartz wafer, a metal sheet, or a substrate modified with other materials. Before step S2, the substrate surface patterning method further includes cleaning, activating, and hydrophobicating treatments on the substrate. Cleaning can be performed using a cleaning solution, such as water, to remove dirt and other contaminants from the substrate surface. Activation can be performed using oxygen plasma to activate the substrate, ensuring good subsequent bonding with molecules in the modification layer. The hydrophobic treatment also forms a hydrophobic material (not shown) on the surface of the substrate 10, such as hexamethyldisilazane (HMDS) formed by vapor deposition. Alternatively, complementary layers such as a spin-on-carbon (SOC), a spin-on-glass (SOG), or a bottom anti-reflection coating (BARC) can be applied to the substrate 10 (not shown).

[0115] The purpose of step S2 is to modify the surface of the substrate 10 to have group A on its surface. The surface roughness of the modified layer 30 is less than 2 nm. Group A may be at least one of the following end groups, including: azide (—N3), alkenyl (—CH=CH2), aldehyde (—CHO), epoxy (—CH(O)CH—), mercapto (—SH), substituted or unsubstituted amino (—NH2), alkynyl (CH≡C—), ester (-COOR), carboxylic acid (—COOH), halogen group, hydroxyl (—OH), cyanate group (—OC≡N), thiocyanate group, isothiocyanate group, and groups used as multidentate ligands (e.g., crown ether, cyclodextrin, EDTA group, etc.).

[0116] In one embodiment, the chemical formula of the modification layer 30 before exposure is: A-C a H b X c— E, wherein X is one or more of the third, fourth, fifth, sixth, and seventh main groups, wherein 45 > a > 1, 90 > b > 1, and 90 > c > 0; the group E is a molecular group having an end group, which includes but is not limited to an amino group (— NH2, — NH) end group, a mercapto group (— SH) end group, and a hydrolyzable end group into a silicon hydroxyl group (— Si(OR)2, — Si(OR)3, — SiCl2, — SiCl3) or a hydroxyl group (— OH). The group E can react with the substrate 10, fix the molecule on the substrate 10, and expose the group A that can undergo a bonding reaction on the surface of the substrate.

[0117] In one embodiment, the step S2 includes dissolving the material particles having the group A in a suitable solvent to form a solution with a suitable concentration, coating the material particles on a surface of the substrate 10 through a spin coating process, and solidifying the material particles to form the modification layer 30. For example, a 4-inch substrate is usually coated with 1-5 ml of the solution of the material particles. It is understood that a baking step at a temperature of 60-200 °C for 20-120 seconds or a step of irradiation by ultraviolet or infrared light can be optionally added after the spin coating to attach the end group A to the surface of the substrate 10 and remove the residual solvent and the unattached small molecules to avoid defects in the subsequent steps.

[0118] It is understood that the residual solvent in the modification layer 30 and the discrete molecules that are not attached to the surface of the substrate 10 can be removed at room temperature or at a high temperature under a low pressure or a vacuum environment before the step S3 is performed to avoid outgassing during the exposure of the modification layer 30 or the low pressure or vacuum exposure.

[0119] Alternatively, in another embodiment, the step S2 includes depositing the material particles having the end group A that can undergo a bonding reaction on a surface of the substrate 10 to form the modification layer 30 by a vapor deposition method, such as a physical vapor deposition method or a chemical vapor deposition method.

[0120] The thickness of the modification layer can be 0.1 nm-100 nm. It is understood that the modification layer 30 can be a monomolecular film or a multilayer film. The formation of the modification layer 30 can be performed by multiple spin coating or multiple deposition in the step S2, but is not limited to the spin coating or the deposition.

[0121] In this embodiment, the step S3 includes exposing the modification layer 30 to light, such as ultraviolet light, to form a modified layer 30' having the group A that can undergo a bonding reaction on the surface of the substrate 10. Figure 4As shown, during exposure, one side of the modification layer 30 is provided with a mask plate 60 with pattern information to achieve partial exposure and partial non-exposure of the modification layer 30. The exposure of the modification layer 30 uses soft X-ray with any single wavelength or mixed wavelength in the range of 1-15 nm, or uses electron beam without the mask plate.

[0122] In one embodiment, the mask plate 60 is provided with through holes 61 for the soft X-ray (high-energy ray) to pass through to the modification layer 30, or uses electron beam to expose the modification layer 30 without the mask plate. The energy of the high-energy ray is lower than 30 mJ / cm 2 After exposure, the modification layer 30 is formed with exposed portions 31 and non-exposed portions 33. Thus, the pattern of the through holes 61 of the mask plate 60 is transferred to the modification layer 30 and corresponds to the exposed portions 31, i.e. the pattern of the through holes 61 is consistent with the pattern of the exposed portions 31. The exposed portions 31 undergo chemical change and no longer contain the group A, i.e. the group A is transformed into group B which no longer has the function of bond reaction.

[0123] The mask plate 60 has pattern information, which is provided to make the light irradiating the modification layer 30 finally have the pattern information of the mask plate so as to locally expose the modification layer 30. In other embodiments, the mask plate is provided with micro-holes (not shown in the figure). Light (soft X-ray) passes through the micro-holes to form a specific interference pattern of light to the modification layer 30 so as to locally expose the modification layer 30. Or light (soft X-ray) is reflected by the mask plate to the modification layer 30 so as to locally expose the modification layer 30. Or light (soft X-ray) is transmitted or reflected by the mask plate and then reaches the modification layer 30 through a certain optical path system (not shown in the figure) so as to locally expose the modification layer 30.

[0124] In one embodiment, as shown in Figure 5 Step S4 includes forming the characteristic particle layer 50 on the partially exposed modification layer 30. The forming method can use spin coating method or vapor deposition method, etc. The characteristic particles in the characteristic particle layer 50 have group C which can bond with group A in the modification layer 30.

[0125] It can be understood that after step S4 and before step S5, the substrate surface patterning method can further include: using heating baking, ultraviolet or infrared irradiation to promote the bond reaction between the characteristic particles in the characteristic particle layer 50 and the group A of the modification layer. For example, heating in the temperature range of 90-200 °C for 20 minutes, or selecting ultraviolet or infrared light exposure in the whole sample area for 20 minutes, etc. to promote the bond reaction.

[0126] It is understood that the thickness of the layer of characteristic particles 50 can be controlled by selecting one or more bonding reactions. Since there can be unreacted groups A in the modification layer 30 after one bonding reaction, the number of bonding reactions between the characteristic particles and the modification layer 30 can be increased, and the characteristic particles in different bonding reaction pairs can be the same or different.

[0127] The portion of the layer of characteristic particles 50 covering the unexposed portion 33 is firmly bound to the modification layer 30 because the groups C of the characteristic particles have reacted with the groups A of the unexposed portion 33. The portion of the layer of characteristic particles 50 covering the exposed portion 31 is only physically adsorbed on the modification layer 30 because the groups C of the characteristic particles cannot react with the groups B of the exposed portion 31.

[0128] The layer of characteristic particles 50 is rinsed with a suitable developing solution in step S5. The portion of the layer of characteristic particles 50 covering the exposed portion 31 is washed away because it is only physically adsorbed on the modification layer 30. The portion of the layer of characteristic particles 50 covering the unexposed portion 33 is not washed away because it is firmly bound to the modification layer 30 by chemical bonding, and thus remains to form a patterned layer of characteristic particles 50, as shown in Fig. 2B. Figure 5

[0129] ​The developer used in step S5 to dissolve and remove the characteristic macromolecules of the characteristic particle layer 50 which have not undergone the bonding reaction can be an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 0.5 to 5%, or an organic solvent such as a ketone, an alcohol, etc., for example, cyclohexanone and methyl-2-n-amyl ketone; an alcohol such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; an ether such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether; an ester such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, and propylene glycol mono-t-butyl ether acetate; and a lactone such as γ-butyrolactone; a high-boiling alcohol solvent such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, or 1,3-butanediol; or a developer formed by mixing one or more of the above solvents. The developer is brought into contact with the characteristic particle layer 50 for a period of 20 to 120 seconds.

[0130] It is to be understood that after step S5, a rinsing process with water can optionally be added, and the rinsing time is 20 to 120 seconds. Then, a baking process can optionally be added, and the baking temperature is 60 to 200°C, and the baking time is 20 to 120 seconds, to remove the residual developer on the surface.

[0131] The resolution of the patterned characteristic particle layer 50 thus obtained is 3 to 100 nm, and the edge roughness is 2 to 30% of the pattern resolution.

[0132] The characteristic particles contained in the characteristic particle layer 50 can be an etch-resistant material or a dielectric material. The molecular size of the characteristic particles is preferably 0.2 to 20 nm. The thickness of the characteristic particle layer 50 can be 0.2 to 200 nm.

[0133] When the characteristic particles are an etch-resistant material, the substrate surface patterning method further comprises: using the characteristic particle layer 50 as a mask, etching the areas of the substrate 10 not covered by the characteristic particle layer 50 with an etchant to transfer the pattern to the substrate 10. During the etching process, the characteristic particle layer 50 is not etched, so the areas covered by the characteristic particle layer 50 are not etched, while the areas of the modification layer 30 and the substrate 10 not covered by the characteristic particle layer 50 are etched. After the etching is completed, the characteristic particle layer 50 and the modification layer 30 on the substrate 10 are removed, and a patterned substrate 10 is obtained, as shown in FIG. 2. Figure 5

[0134] ​When the characteristic particles are molecules of a dielectric material, the layer 50 of characteristic particles can remain as a dielectric functional layer on the surface of the substrate 10, in which case the step of etching the substrate 10 is not required.

[0135] The substrate surface patterning method of the present application uses simple materials, can achieve high resolution, and can form a pattern with low pattern edge roughness. The substrate surface patterning method of the present application can be applied to chip manufacturing technology at a 5 nm process node and below.

[0136] The substrate surface patterning method of the present application uses a light source with a wavelength of 1-15 nm or an electron beam to selectively damage the functional end groups of a monomolecular / multimolecular modification layer on a substrate, and uses functional characteristic nanoparticles (including stereoscopic structure macromolecules) with a particle size of 0.2-20 nm to perform a bonding reaction with the unexposed modification layer, thereby forming a functional (including etch resistance, special dielectricity, etc.) pattern with low exposure energy requirement, high resolution, and low pattern edge roughness.

[0137] The technical solutions of the embodiments of the present application are further described below through specific examples.

[0138] Embodiment 1

[0139] Steps (a) and (b) are for preparing the material (trichlorosilane) of the modification layer.

[0140] (a) In a three-necked flask, one equivalent of p-fluorobenzene dicarboxaldehyde, 2.4 equivalents of methyl triphenyl phosphonium bromide, and 2.9 equivalents of potassium tert-butoxide (BuOK) were added in anhydrous and oxygen-free tetrahydrofuran (THF) solvent under argon protection at room temperature, and stirred for 4 hours. After rotary evaporation, the obtained organic layer was extracted with water and diethyl ether, dried with MgSO4, dissolved in n-hexane, concentrated by rotary evaporation, and purified by a color column to obtain p-fluorobenzene diene with a yield of nearly 75%.

[0141] (b) In a two-necked flask, 1.2 equivalents of trichlorosilane and 1 equivalent of p-fluorobenzene diene were reacted in THF solvent under the condition of 0.04 equivalents of H2PtCl6 catalyst, and refluxed at 80°C for 6 hours. After vacuum distillation, trichlorosilane monomer was obtained with a yield of nearly 90%.

[0142] The synthetic route of step (a) is shown in the following reaction formula:

[0143]

[0144] The synthetic route of step (b) is shown in the following reaction formula:

[0145]

[0146] (c) providing a 2-inch silicon substrate, cleaning the silicon substrate with a Piranha solution (a mixture of concentrated sulfuric acid and 30% hydrogen peroxide (7:3)), activating the surface of the silicon substrate with O2 plasma, and reacting the activated silicon substrate with 2 ml of trichlorosilane at 80°C under vacuum for 2 h to form a modification layer on the silicon substrate. SEM-EDX testing showed that the surface of the silicon substrate was modified with F-containing groups, indicating that trichlorosilane had been formed on the silicon substrate.

[0147] (d) using a mask plate with a line via pattern (the width of the line via is 100 nm, and the pitch between two adjacent line vias is 100 nm) and soft X-ray with a wavelength of 13.5 nm (energy of 30 mJ / cm 2 ) for exposure, so that the double bonds of trichlorosilane exposed on the surface of the silicon substrate are damaged.

[0148] (e) preparing a characteristic particle material: using a mercapto-siloxane monomer, adding 1.6 equivalents of anhydrous FeCl3, 2 equivalents of concentrated hydrochloric acid in a three-necked flask, dissolving in a mixed solvent of methanol, petroleum ether, and dichloromethane at a volume ratio of 2:4:1 with mechanical stirring. One equivalent of the mercapto-siloxane monomer was dissolved to form a 10% petroleum ether solution. The mercapto-siloxane monomer solution was added dropwise to the three-necked flask through a constant-pressure funnel within 10 h, and was stirred at room temperature for 24 h, and then reacted at 60°C for 10 h. After sufficient reaction, the mixture was filtered and separated, and the upper organic layer was transferred to a round-bottom flask, and sodium carbonate and calcium chloride were added to remove acid, and stirred for 12 h, filtered, and the filtrate was concentrated under reduced pressure using a rotary evaporator, and was placed in a 4°C refrigerator for crystallization. The precipitated crystals were recrystallized with a dichloromethane and ethanol mixed solution to obtain the target product mercapto-silsesquioxane (characteristic particle material).

[0149] The synthesis reaction formula of mercapto-silsesquioxane is as follows:

[0150]

[0151] wherein the R group is:

[0152] (f) coating the characteristic molecular solution obtained in (e) on the silicon substrate prepared in (d), and then irradiating the whole silicon substrate with ultraviolet light with a wavelength of 365 nm for 120 s, so that the mercapto group of the characteristic particle and the double bond of the modification layer are fully reacted, thereby fixing the mercapto-silsesquioxane (characteristic particle) on the silicon substrate.

[0153] (g) washing with an alcohol developer to remove the mercapto-silsesquioxane (characteristic particle) that does not undergo bonding reaction, to obtain an etch-resistant single-layer structure.

[0154] It can be understood that there can still be a large number of thiol end groups in the characteristic particle layer that have not reacted. If necessary, other film layers can be constructed on the existing structure by continuing to perform the bottom-up construction.

[0155] Technical effects of example 1

[0156] Example 1 uses a new type of chlorosilane monomer to functionally modify the surface of a silicon-based substrate. The silicon-chlorine part reacts with the silicon-based substrate, and the double bond group is exposed on the surface of the silicon-based substrate. After soft X-ray exposure, the double bond is selectively changed. The changed part no longer reacts with the nano-scale polyoctasilsesquioxane with thiol as the main material structure. Only the unexposed part can react with the nano-scale polyoctasilsesquioxane with thiol. The molecular size of the nano-scale polysiloxane is between 0.3 and 0.7 nm, forming a film layer pattern with a thickness of about 1 nm. The molecule has high etch resistance and can exhibit etch resistance selectivity under O ion etching. Moreover, the molecule has multiple thiol groups that do not participate in bonding reactions, and on this basis, the film layer thickness can be increased by continuing to perform the bottom-up construction, thereby achieving higher etch resistance or other functionality.

[0157] Example 2

[0158] The silicon-based substrate with a modified layer is obtained by performing steps (a), (b), (c), and (d) of Example 1.

[0159] (e) In the reactor, add 1 equivalent of hafnium isopropoxide isopropyl alcohol compound and 4 equivalents of 3-mercaptoisobutyric acid in butanol. Stir at room temperature for 1 h. After stirring the obtained mixture at 75℃ for 24 h, cool the reaction solution and place it in a 4℃ environment for 72 h to crystallize. Filter to obtain crystal thiol hafnium cluster crystals.

[0160] The synthesis reaction formula of the hafnium cluster crystal is as follows:

[0161]

[0162] (f) Dissolve the thiol hafnium crystal in chloroform to obtain a solution, and coat it on the silicon-based substrate prepared in (d). Place the entire substrate under ultraviolet light with a wavelength of 365 nm for 120 s to allow the thiol of the characteristic particle and the double bond of the modified layer to fully react, thereby fixing the thiol hafnium cluster (characteristic particle) on the silicon-based substrate.

[0163] (g) Wash with chloroform developer to remove the functional thiol hafnium cluster that has not undergone bonding reaction. Remove the organic group at high temperature to obtain an ultra-thin high-dielectric constant hafnium cluster molecular layer structure. If necessary, other film layers can be constructed on the existing structure by continuing to perform the bottom-up reaction based on the thiol reaction, thereby adjusting the film layer thickness.

[0164] Technical effects of example 2

[0165] In Example 2, a new chlorosilane monomer is used to functionalize the surface of a silicon substrate, in which the silicon-chlorine moiety reacts with the silicon substrate and the double bond group is exposed on the surface of the silicon substrate. After soft X-ray exposure, the double bond is selectively changed, and the changed moiety no longer reacts with the nanoscale polyoctasilsesquioxane with a thiol group. Only the unexposed moiety can react with the hafnium oxide cluster macromolecule with a thiol group. The hafnium oxide cluster macromolecule has good high dielectric properties and can remain on the surface of the silicon substrate as a functional molecular layer with high dielectric constant. The molecular size is between 0.3 and 0.7 nm, and a film layer pattern with a thickness of about 1 nm is formed, which can be used as a dielectric layer with high dielectric constant. In addition, the molecule has multiple thiol groups that do not participate in the bonding reaction, and the film layer thickness can be further increased from bottom to top on this basis to achieve the best functional properties.

[0166] The substrate surface patterning method of the present application requires very low exposure energy in the exposure process, saves exposure energy, and can almost avoid chemical reaction diffusion and secondary electron diffusion in the film layer. In addition, the substrate surface patterning method of the present application can form a high-resolution pattern, which has better patterning effect than traditional patterning material processes and fundamentally avoids the requirement of high sensitivity of the patterning material. In addition, compared with the complex process method for forming a film layer with high dielectric constant, the substrate surface patterning method saves material and can form an extremely thin film layer.

[0167] It should be noted that the above is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto. Any person skilled in the art can easily think of changes or replacements within the technical scope disclosed in the present application, which should be covered within the protection scope of the present application. In the case of no conflict, the embodiments and features in the embodiments can be combined with each other. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A semiconductor device, characterized by, The semiconductor device comprises: a substrate; a modification layer on a surface of the substrate, the modification layer being locally exposed, the modification layer comprising exposed portions and unexposed portions, the unexposed portions of the modification layer having a group A, and the exposed portions of the modification layer having a group B formed by the group A being exposed; and a patterned characteristic particle layer on the surface of the modification layer away from the substrate and covering the unexposed portions of the modification layer, the characteristic particle layer having a group C capable of bonding with the group A without reacting with the group B, the characteristic particle layer being bonded with the unexposed portions of the modification layer through the bonding of the group A and the group C, The material of the unexposed parts of the modification layer has the chemical formula: A - C a H b X c — E, wherein X is one or several of the third, fourth, fifth, sixth, seventh main group elements, wherein 45 > a > 1, 90 > b > 1, 90 > c > 0; the group E is a molecular group containing a terminal group, which is at least one of the following: amino type terminal group, mercapto type terminal group, terminal group hydrolysable to silanol or hydroxyl; when the group A is an azido group and the group B is an amino group; when the group A is an alkenyl group and the group B is an alkyl group; when the group A is an aldehyde group and the group B is a hydroxyl group; when the group A is an epoxy group and the group B is a hydroxyl group. when said group A is , said group B is ; when said group A is , said group B is .

2. The semiconductor device according to claim 1, wherein when said group A is an azido group, said group C is an alkynyl group or ; when the group A is an alkenyl group and the group C is a mercapto group; when the group A is an aldehyde group and the group C is H2N— O— ; when said group A is , said group C is or an alkenyl group linked to an unsaturated group; when the group A is an epoxy group and the group C is an amino group.

3. The semiconductor device of claim 1, wherein The substrate is a silicon wafer, a quartz wafer or a metal sheet, or the substrate is a substrate obtained by adding other materials to a silicon wafer, a quartz wafer or a metal sheet.

4. The semiconductor device of claim 1, wherein The characteristic particle layer is a dielectric material layer.

5. The semiconductor device of claim 1, wherein The characteristic particle layer contains characteristic particles having the group C, and the characteristic particles have a molecular size of 0.2-20 nm.

6. A terminal, characterized by comprising: The semiconductor device comprises a housing and a semiconductor device accommodated in the housing, and the semiconductor device comprises the semiconductor device according to any one of claims 1-5.

7. A method of patterning a surface of a substrate, the method comprising: The semiconductor device comprises: providing a substrate; forming a modification layer on a surface of the substrate, the modification layer having a group A, and the group A being exposed on the surface of the substrate; locally exposing the modification layer by using a soft X-ray of any single wavelength or a mixed wavelength in a wavelength range of 1-15 nm, or by using an electron beam, so that the group A of the exposed portions of the modification layer is changed to form a group B; forming a characteristic particle layer on the modification layer, the characteristic particles in the characteristic particle layer having a group C capable of bonding with the group A without reacting with the group B; and removing the portions of the characteristic particle layer not reacting with the modification layer by using a developing solution, The material of the modification layer before the local exposure of the modification layer has the chemical formula: A-C a H b X c -E, wherein X is one or several of the third, fourth, fifth, sixth and seventh main group elements, wherein 45 >= a >= 1, 90 >= b >= 1, 90 >= c >= 0; the group E is a molecular group containing a terminal group, the terminal group being at least one of the following: an amino type terminal group, a mercapto type terminal group, a terminal group hydrolysable to a silicon hydroxyl group or a hydroxyl group; when the group A is an azido group and the group B is an amino group; when the group A is an alkenyl group and the group B is an alkyl group; when the group A is an aldehyde group and the group B is a hydroxyl group; when the group A is an epoxy group and the group B is a hydroxyl group. when said group A is , said group B is ; when said group A is , said group B is .

8. The method of claim 7, wherein The characteristic particle layer contains an etch-resistant material or a dielectric material.

9. The method of claim 7, wherein The characteristic particle layer contains characteristic particles having the group C, and the characteristic particles have a molecular size of 0.2-20 nm.

10. The method of claim 7, wherein The characteristic particle is an etch-resistant molecule; and the substrate surface patterning method further comprises etching the regions of the substrate not covered by the characteristic particle layer to transfer a pattern to the substrate.

11. The method of claim 10, wherein The step of locally exposing the modification layer by soft X-rays uses a mask plate, and the soft X-rays with pattern information passing through the mask plate reach the modification layer to locally expose the modification layer.

12. The method according to claim 7, wherein The substrate surface patterning method further comprises baking or irradiating the characteristic particle layer by ultraviolet or infrared to promote the bonding reaction between the group C of the characteristic particles in the characteristic particle layer and the group A of the modification layer.

13. The method of claim 7, wherein The developing solution is a tetramethylammonium hydroxide solution, a ketone organic solvent, an alcohol organic solvent, an ether organic solvent, an ester organic solvent, or a lactone organic solvent.

14. An electronic device comprising an integrated circuit, characterized in that The integrated circuit includes the semiconductor device of any one of claims 1 to 5.

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