Field-assisted thermal cycle vapor deposition of HZO films

Abstract

A method for forming a film comprising hafnium, zirconium and oxygen, the method comprising forming (100) a film by a cyclic vapor deposition process under the action of an electric field (13).

Description

Technical Field

[0001] The present invention relates to the field of thermal cycle vapor deposition, and more particularly to the creation of films containing hafnium, zirconium and oxygen. Background Art

[0002] Ferroelectric memory devices show great potential in high-speed read and write operations, low power consumption, and high retention. Hafnium oxide-based films have emerged as promising materials for ferroelectric memory applications, providing excellent compatibility with complementary metal oxide semiconductor (CMOS) manufacturing processes.

[0003] However, conventional deposition methods for hafnium oxide-based thin films often result in multiphase films with inconsistent ferroelectric properties, leading to non-uniform device performance.

[0004] CN111554568 describes a method for preparing a hafnium oxide based film, wherein the doped hafnium oxide film is believed to have ferroelectric properties. Other elements mentioned for doping include Zr and the like. The method comprises depositing a hafnium oxide based film on a substrate and annealing it in an electric field using an annealing device. During the annealing process, an electric field is selectively applied at different time periods, including during heating, holding temperature, and cooling. The application of an electric field helps to control the energy field during the crystallization of the film, thereby improving the quality and uniformity of the ferroelectric film.

[0005] However, the method requires many steps, including depositing a hafnium oxide-based thin film on a substrate, providing the film in a deposition tool, applying a capping layer on the film surface, providing the capping layer in an electric field device, annealing it in the electric field device for three different time periods (heating, maintaining temperature, and cooling), and selectively applying an electric field during each stage.

[0006] Therefore, there is a need in the art for a streamlined and efficient method and system for producing hafnium zirconium oxide-based ferroelectric thin films. Summary of the invention

[0007] It is an object of the present invention to provide a good method and system for forming films comprising hafnium, zirconium and oxygen.

[0008] The above objects are achieved by the method and system according to the present invention.

[0009] In a first aspect, the present invention relates to a method for forming a film comprising hafnium, zirconium and oxygen, the method comprising forming the film by a thermal cycle vapor deposition process under the action of an electric field.

[0010] In a second aspect, the present invention relates to a thermal cycle vapor deposition system, such as a thermal atomic layer deposition system, comprising a reactor suitable for forming a film comprising hafnium, zirconium and oxygen by thermal cycle vapor deposition, such as by thermal atomic layer deposition, and comprising:

[0011] - an electric field generator configured to generate an electric field during formation of the film; and

[0012] - A controller configured to direct thermal cyclic vapor deposition, such as thermal atomic layer deposition, of a film and to operate an electric field generator to generate an electric field during the thermal cyclic vapor deposition, such as thermal atomic layer deposition.

[0013] In a third aspect, the invention relates to a computer program comprising instructions for causing the system of the second aspect to perform the steps of the method of the first aspect.

[0014] In a fourth aspect, the invention relates to a computer readable medium having stored thereon the computer program of the third aspect.

[0015] An advantage of embodiments of the present invention is that a high quality zirconium-hafnium oxide based film with very good uniformity can be obtained.

[0016] The advantage of the embodiments of the present invention is that an orthorhombic zirconium oxide hafnium-based film with good ferroelectric properties can be obtained.

[0017] An advantage of embodiments of the present invention is that they enable precise control of the deposition process and application of the electric field, thereby enabling the formation of consistent and reproducible films.

[0018] An advantage of embodiments of the present invention is that they enable efficient deposition. In a thermal cycle vapor deposition process, such as a thermal atomic layer deposition process, the use of an electric field facilitates the formation of an orthorhombic phase already during layer deposition. This results in faster orthorhombic film formation, reducing production time and cost.

[0019] Particular and preferred aspects of the invention are set out in the accompanying independent and dependent claims. Features of the dependent claims may be combined with features of the independent claims as appropriate and with features of other dependent claims and not merely as explicitly set out in the claims.

[0020] While there have been continuous improvements, changes and developments in devices in the art, the concepts of the present invention are believed to represent substantially new and novel improvements involving departures from prior practice, thereby providing a more efficient, stable and reliable device of this nature.

[0021] The above and other features, characteristics and advantages of the present invention will become apparent from the following detailed description in conjunction with the accompanying drawings, which illustrate the principles of the present invention by way of example. This description is given for illustrative purposes only and does not limit the scope of the present invention. The reference numbers cited below refer to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figures 1 to 5 A flow chart of a method according to an embodiment of the present invention is shown.

[0023] Figure 6 and Figure 7 A schematic diagram of a thermal cycle vapor deposition system according to an embodiment of the present invention is shown.

[0024] Figure 8 A schematic diagram of a substrate holder suitable for use in a thermal cycle vapor deposition system of the present invention is shown.

[0025] The same reference numbers in different drawings identify the same or similar elements. DETAILED DESCRIPTION

[0026] The present invention will be described with respect to specific embodiments and with reference to certain drawings, but the invention is not limited thereto but only by the claims. The drawings described are merely illustrative and non-restrictive. In the drawings, for illustrative purposes, the size of some elements may be exaggerated and not drawn to scale. The sizes and relative sizes do not correspond to actual reductions in the practice of the invention.

[0027] In addition, the terms first, second, third, etc. in the specification and claims are used to distinguish similar elements and are not necessarily used to describe a sequence in time, space, order or any other manner. It should be understood that the terms so used are interchangeable under appropriate circumstances, and the embodiments of the invention described herein are capable of operating in other sequences than those described or shown herein.

[0028] It should be noted that the term "comprising" used in the claims should not be interpreted as being limited to the means listed thereafter; it does not exclude other elements or steps. Therefore, it should be interpreted as specifying the presence of the features, integers, steps or components mentioned, but not excluding the presence or addition of one or more other features, integers, steps or components or combinations thereof. Therefore, the term "comprising" covers the case where only the features are present (which can therefore always be replaced by "consisting of..." in order to limit the scope to the stated features) as well as the case where these features and one or more other features are present. Therefore, as an embodiment, the word "comprising" according to the present invention also includes the absence of other components. Therefore, the scope of the expression "device comprising means A and B" should not be interpreted as being limited to devices consisting only of components A and B. This means that for the present invention, the only relevant components of the device are A and B.

[0029] Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, the phrases "in one embodiment" or "in an embodiment" appearing in various places in this specification do not necessarily all refer to the same embodiment, but may refer to the same embodiment. Furthermore, in one or more embodiments, the particular features, structures, or characteristics may be combined in any suitable manner, as will be apparent to one of ordinary skill in the art from this disclosure.

[0030] Similarly, it should be understood that in the description of exemplary embodiments of the present invention, various features of the present invention are sometimes combined in a single embodiment, figure, or description thereof for the purpose of simplifying the disclosure and aiding in the understanding of one or more various inventive aspects. However, this method of disclosure should not be interpreted as reflecting an intention that the claimed invention requires more features than those expressly recited in each claim. On the contrary, as reflected in the following claims, the inventive aspects are less than all the features of a single preceding disclosed embodiment. Therefore, the claims following the detailed description are hereby expressly incorporated into the detailed description, with each claim independently serving as a separate embodiment of the present invention.

[0031] In addition, although some embodiments described herein include some but not other features included in other embodiments, the combination of features of different embodiments is meant to be within the scope of the present invention and form different embodiments, as will be understood by those skilled in the art. For example, in the following claims, any of the claimed embodiments can be used in any combination.

[0032] In addition, some embodiments are described herein as methods or combinations of elements of methods that can be implemented by a processor of a computer system or by other devices that perform the function. Therefore, a processor with necessary instructions for performing such methods or method elements forms a device for performing such methods or method elements. In addition, the elements of the device embodiments described herein are examples of devices for performing the functions performed by the elements, with the purpose of realizing the present invention.

[0033] In the description provided herein, many specific details are set forth. However, it should be understood that embodiments of the present invention can be implemented without these specific details. In other cases, well-known methods, structures, and techniques are not shown in detail to avoid obscuring the understanding of this specification.

[0034] Reference now Figure 1-5 ,in particular Figure 1 In a first aspect, the invention relates to a method 100 for forming a film comprising hafnium, zirconium and oxygen, the method comprising forming the film by a thermal cyclic vapor deposition process under the influence of an electric field 13, for example by thermal atomic layer deposition.

[0035] The membrane may have any surface area, but the method of the first aspect is particularly suitable for forming membranes of large surface area, especially uniform membranes of large surface area. In embodiments, the surface area of ​​the membrane may be measured to be at least 300 cm 2 , preferably at least 700cm 2 .

[0036] The film produced by the method according to the first aspect typically has ferroelectric properties. In other words, it is typically a ferroelectric film.

[0037] Films produced according to the method of the first aspect typically have a crystallinity of at least 50% orthogonal, preferably at least 60% orthogonal, more preferably at least 70% orthogonal, still more preferably at least 80% orthogonal, most preferably at least 90% orthogonal.

[0038] The film produced by the method according to the first aspect is generally uniform in its surface and thickness.

[0039] The membrane produced by the method according to the first aspect typically has a k value of at least 40, preferably at least 50.

[0040] The film comprises hafnium, zirconium and oxygen. In an embodiment, the atomic ratio of hafnium to zirconium may be from 40:60 to 60:40, preferably from 45:55 to 55:45. Most preferably, it is 50:50.

[0041] In an embodiment, the cations present in the membrane may consist of at least 95%, preferably at least 99%, and most preferably 100% hafnium and zirconium. Examples of other cations that may enter the membrane composition are Si, Al, La, Y, N, Gd, Sr, Ce, Fe, Sc, Ge, Lu, Ta, and Ti, among others.

[0042] In an embodiment, the anions present in the membrane may consist of at least 95%, preferably at least 99%, and most preferably 100% oxygen. Examples of other anions that may enter the membrane composition are N, S, F, and the like.

[0043] The atomic ratio between anions and cations in the membrane is generally 1.9 to 2.1, preferably 2.0.

[0044] In a preferred embodiment, the composition of the membrane may consist of anions and cations in an atomic ratio of 1.9 to 2.1, wherein at least 95% of the cations are a mixture of hafnium and zirconium in an atomic ratio of 40:60 to 60:40, and wherein at least 95% of the anions are oxygen anions.

[0045] In a more preferred embodiment, the composition of the membrane may consist of anions and cations in an atomic ratio of 2, wherein at least 95% of the cations are a mixture of hafnium and zirconium in an atomic ratio of 40:60 to 60:40, and wherein at least 99% of the anions are oxygen anions.

[0046] In an even more preferred embodiment, the composition of the membrane may consist of anions and cations in an atomic ratio of 2, wherein at least 95% of the cations are a mixture of hafnium and zirconium in an atomic ratio of 45:55 to 55:45, and wherein at least 99% of the anions are oxygen anions.

[0047] In an even more preferred embodiment, the composition of the membrane may consist of anions and cations in an atomic ratio of 2, wherein at least 99% of the cations are a mixture of hafnium and zirconium in an atomic ratio of 45:55 to 55:45, and wherein at least 99% of the anions are oxygen anions.

[0048] In the most preferred embodiment, the composition of the film is Hf 0.5 Zr 0.5 O2.

[0049] The method of the first aspect includes forming 100 a film by a thermal cycle vapor deposition process.

[0050] As used herein, a cyclic vapor deposition process refers to the sequential introduction of gaseous precursors and / or reactants into a chamber of a reactor to deposit layers on a substrate.

[0051] A thermal cycle vapor deposition process is a cyclic vapor deposition process in which precursors and / or reactants are sequentially introduced into a chamber of a reactor to deposit a layer on a substrate heated to a temperature conducive to allowing the precursors and / or reactants to react on the deposition surface of the substrate. The term "thermal" means that the heating of the substrate enables the precursors and / or reactants to react on the deposition surface. This is in contrast to a "plasma enhanced" cyclic vapor deposition process in which the use of a plasma allows the precursors and / or reactants to become active species, such as ions or free radicals that react on the deposition surface of the substrate. In thermal cycle vapor deposition, plasma assistance is not used to form the layer. In other words, the thermal cycle vapor deposition process does not include exposing the substrate to active species, such as ions or free radicals, generated in the plasma.

[0052] In an embodiment, the thermal cyclic vapor deposition process is selected from thermal atomic layer deposition (ALD), cyclic chemical vapor deposition (cyclic CVD), and a hybrid cyclic deposition process. The hybrid cyclic deposition process includes at least one thermal ALD cycle and one cyclic CVD cycle.

[0053] In some embodiments, the thermal cyclic vapor deposition process includes at least one thermal ALD cycle. A thermal ALD cycle of "n" precursors / reactants is a series of "n" steps, each step including a precursor / reactant pulse followed by a complete purge. A cyclic CVD cycle of "n" precursors / reactants is a series of "n" steps, each step including a precursor / reactant pulse followed by an optional incomplete purge.

[0054] How to perform thermal ALD is well known to those skilled in the art. Briefly, thermal ALD involves the cyclic, iterative introduction of two or more precursor gases. Each precursor is introduced separately into a deposition chamber in a prescribed order. As each precursor is introduced, it reacts with the heated substrate surface in a process known as chemisorption, ideally in a self-limiting manner, forming at most a monolayer. This chemisorption is promoted by increasing the temperature of the substrate, ideally high enough to enable surface reactions but not so high as to cause decomposition or gas phase reactions of the precursor. Between the introduction of each precursor, the chamber is purged with an inert gas or vacuum to ideally remove any unreacted precursor reaction byproducts. This ensures that the next precursor ideally reacts only with the chemisorbed layer on the substrate surface and not with other precursors in the gas phase. This series of steps—precursor pulse, purge, next precursor pulse, purge—is repeated in a repetitive manner. Each cycle deposits a new atomic layer on the substrate, and the number of cycles determines the thickness of the film. In this way, thin films are gradually built up, one atomic layer at a time. However, it is well understood by those skilled in the art that the actual implementation of thermal ALD can sometimes deviate from this idealized process due to various factors. For example, in order to optimize yield, the process can be run outside the standard temperature window of thermal ALD. This may cause some precursor surface decomposition to occur, resulting in the process not being completely self-limiting. However, since the cycle of "n" precursors / reactants is still a series of "n" steps of the process, each step including a precursor / reactant pulse and a subsequent full purge, it is still thermal ALD. In addition, the purge time of the ALD process can be minimized, again optimizing yield, which may result in some degree of gas phase reaction between the precursors. Here, since the purge is not completed, the process is referred to as a CVD process.

[0055] In some cases, the reactants can physically adsorb onto the surface, catalyzing the decomposition of the pulsed precursors. This can result in an exponential decay in the growth rate over time during each precursor pulse. While this process deviates from idealized ALD, it is still an ALD process in that it cycles through “n” precursor / reactants, a series of “n” steps, each consisting of a precursor / reactant pulse followed by a full purge.

[0056] How to perform cyclic CVD is also well known to those skilled in the art. In short, cyclic CVD includes the cyclic, iterative introduction of two or more precursor gases. Each precursor is introduced into the deposition chamber separately in a specified order. When each precursor is introduced, it reacts with the heated substrate surface, a process called chemical adsorption to form a layer. This chemical adsorption is promoted by increasing the temperature of the substrate, which is carefully controlled to be high enough to enable surface reactions, but not high enough to cause decomposition or gas phase reactions of the precursor. Between the introduction of each precursor, the chamber is not purged or incompletely purged with an inert gas or vacuum to remove some of the unreacted precursors and some of the reaction byproducts. This ensures that the next precursor reacts with both the chemical adsorption layer on the substrate surface and other precursors in the gas phase. The sequence of these steps—precursor pulse, optional partial purge, next precursor pulse, optional partial purge—is repeated in an iterative manner. Each cycle deposits a new layer on the substrate, and the thickness of the film is determined by the number of pulses and the duration of each pulse. Most preferably, the method of the first aspect includes forming 100 films by thermal atomic layer deposition.

[0057] In an embodiment, forming 100 a film by thermal cycle vapor deposition may include:

[0058] a. providing 101 a substrate on a holder in a chamber of a reactor of a thermal cycle vapor deposition system (eg, an atomic layer deposition system), the chamber comprising:

[0059] (i) gas distribution system;

[0060] (ii) a holder for the substrate,

[0061] b. heating the substrate 102 to a temperature conducive to allowing the hafnium precursor, the zirconium precursor, and the oxygen source to react on the deposition surface of the substrate to form a film;

[0062] c. Introducing 103 a hafnium precursor, a zirconium precursor, and an oxygen source into the chamber one or more times in a predetermined sequence via a gas distribution system, thereby allowing reactions on the heated deposition surface of the substrate to form a film.

[0063] In an embodiment, the method may include heating 102 the substrate during film formation, typically to a temperature of 100° C. to 600° C.

[0064] In a first aspect, the film is formed under the action of an electric field.

[0065] In embodiments, the electric field may be direct current, alternating current, or a combination of both.

[0066] Preferably, the electric field may be a DC electric field.

[0067] In an embodiment, the DC electric field may be a pulsed DC electric field. In other embodiments, the DC electric field may be a constant field.

[0068] In an embodiment, the pulsed DC electric field may be pulsed at a frequency of 0.5 to 10 Hz.

[0069] In an embodiment, the electric field may be uniformly distributed (e.g., uniformly distributed) over the deposition surface of the substrate on which the film is formed. This means that the electric field is uniform over at least a portion of the substrate surface on which the film is formed. Preferably, the electric field is uniform over 50% or more, preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, even more preferably 90% or more of the top surface of the substrate. Most preferably, the electric field is uniform over the entire top surface of the substrate, except for minor edge effects.

[0070] In an embodiment, the electric field may be perpendicular to the deposition surface of the substrate on which the film is formed.

[0071] In an embodiment, the electric field may be uniformly distributed on and perpendicular to the deposition surface of the substrate on which the film is formed.

[0072] In an embodiment, the electric field may be applied 104 at one or more of the following times:

[0073] During the first precursor pulse; during the optional purge step after the first precursor pulse; during the second precursor pulse, and after a vapor deposition cycle (e.g., between two ALD cycles, between two cyclic chemical vapor deposition cycles, or between an ALD cycle and a cyclic chemical vapor deposition cycle).

[0074] In embodiments using ALD, the electric field 104 may be applied at one or more of the following times:

[0075] During the first precursor pulse; during the purge step after the first precursor pulse; during the second precursor pulse, and after an ALD cycle (e.g., between two ALD cycles).

[0076] In an embodiment, the electric field may have a magnitude from 0.1 MV / cm to the breakdown field of the film.

[0077] In embodiments, when the film thickness exceeds 10 nm, the electric field preferably has a magnitude from 0.1 MV / cm to 5 MV / cm. In other embodiments, when the film thickness is 10 nm or less, the electric field preferably has a magnitude from 0.1 MV / cm to 6 MV / cm.

[0078] In an embodiment, the deposition surface may measure at least 300 cm 2 .

[0079] In an embodiment, the deposition surface may measure at least 700 cm 2 .

[0080] In an embodiment, forming 100 the film may include:

[0081] a. providing 101 a substrate on a holder in a chamber of a reactor of a thermal cycle vapor deposition system (eg, an atomic layer deposition system), the chamber comprising:

[0082] (i) gas distribution system 6;

[0083] (ii) a first conductive component;

[0084] (iii) a holder 4 for a substrate 5, the holder 4 comprising a second conductive part 16, wherein both conductive parts are adapted to allow the generation of an electric field 13 between the first and second conductive parts 16, uniformly across and perpendicular to the surface of the holder 4 holding the substrate 5;

[0085] b. heating the substrate 102 to a temperature conducive to allowing the hafnium precursor, the zirconium precursor, and the oxygen source to react on the deposition surface of the substrate to form a film;

[0086] c. introducing 103 a hafnium precursor, a zirconium precursor, and an oxygen source into the chamber one or more times in a predetermined order via a gas distribution system, thereby allowing a reaction on the heated deposition surface of the substrate to form a film;

[0087] During step c, an electric field 104 is generated, which is uniformly distributed on the surface of the holder supporting the substrate and perpendicular thereto. The method is characterized in that it includes only ALD cycles, only cyclic CVD cycles, or ALD cycles and cyclic CVD cycles.

[0088] The material selected for the substrate may vary depending on the design requirements of the device. It may be a semiconductor such as silicon, germanium, gallium arsenide, gallium nitride, or gallium oxide; for example, it may be a silicon or germanium wafer; alternatively, it may be a metal electrode, such as an electrode made of titanium nitride, tantalum nitride, tungsten, platinum, iridium, or yttrium oxide. In addition, dielectric materials including hafnium oxide, zirconium oxide, silicon dioxide, aluminum oxide, lanthanum oxide, hafnium nitride, or silicon nitride may also be used as substrate materials.

[0089] As is well known to a person skilled in the art of thermal cyclic vapour deposition (e.g. thermal ALD), the holder 4 for the substrate may comprise, in addition to a second conductive member 16 adapted to allow the generation of an electric field, a heating element 7 for heating the substrate. Figure 8 Described in .

[0090] The reactor and its chamber are well known to those skilled in the art of thermal cycle vapor deposition (eg thermal atomic layer deposition).

[0091] The gas distribution system can be any distribution system known to those skilled in the art. For example, it can be a cross-flow gas distribution system or a showerhead gas distribution system.

[0092] If the gas distribution system does not double as an electrode allowing the generation of an electric field between the holder and the gas distribution system, for example if the gas distribution system is a cross-flow gas distribution system, an additional electrode should be used which is suitable for allowing the generation of an electric field 13 uniformly over the surface of the holder 4 and perpendicular thereto. In order to allow the formation of a uniform and perpendicular electric field, the additional electrode is preferably flat, parallel to the top surface of the holder, and large enough to cover the entirety of a typical substrate. For example, the additional electrode may measure at least 300 cm 2 , or at least 700cm 2 .

[0093] Preferably, the gas distribution system and the first conductive component may be identical and may be a showerhead gas distribution system, wherein the first and second conductive components are adapted to allow an electric field to be generated between the holder and the showerhead gas distribution system, and wherein, during step c, an electric field is generated between the holder and the showerhead gas distribution system, the electric field being uniformly distributed over and perpendicular to a surface of the holder supporting the substrate.

[0094] The showerhead distribution system typically includes a gas inlet, a manifold designed to distribute the gas evenly over the entire surface of the showerhead, and a showerhead comprising a plate facing the holder, the plate comprising a plurality of gas outlets connected to the manifold. The holes are designed to produce a uniform gas flow over the substrate. The diameter of the holes can vary, but is typically in the range of 0.5 to 2 mm. The density of the holes in the showerhead can vary, but is typically 1 to 20 holes / cm 2 The showerhead is usually placed close to the holder to ensure uniform exposure of the substrate to the reactant gases. The distance between the showerhead plate and the holder is usually 1 to 5 cm.

[0095] Preferably, the surface of the showerhead gas distribution plate measures at least 300 cm 2 , or at least 700cm 2 , or at least 1500cm 2 , or at least 2000cm 2 , or at least 2500cm 2 , or about 2830cm 2 .

[0096] The use of a showerhead gas distribution system is advantageous for a number of reasons. First, it allows the precursor to be evenly distributed across the substrate. Second, because it is used as one of the electrodes for generating the electric field, and because its shape is typically large enough to overlap the entire substrate, it also allows a uniform electric field to pass evenly across and perpendicular to the surface of the holder 4 holding the substrate 5. Third, because it is used as one of the electrodes, this arrangement simplifies the overall system design and operation because there is no need to install and manage a separate electrode for generating the electric field. Finally, because the substrate heater doubles as one of the electrodes, the system design is simpler and has fewer components. This reduces the chance of contamination of additional components (such as separate electrodes).

[0097] The second conductive component is preferably embedded in the holder.

[0098] In an embodiment, the second conductive component may be a conductive plate, a conductive coil or a conductive grid. Preferably, it is a conductive grid.

[0099] Typically, the reactor includes a voltage controller electrically connected to the showerhead, or if a showerhead is not used, to the first conductive member, and the second conductive member is grounded.

[0100] Reference now Figure 2 In an embodiment, the method may further comprise the step of in-situ annealing 105 the film after film formation.

[0101] In an embodiment, the annealing temperature may be from 300 to 1000° C. In an embodiment, the annealing time may be from 1 second to 1 hour.

[0102] Annealing can be performed on the holder where deposition occurs, or it can be performed in a separate annealing chamber within the reactor.

[0103] Reference now Figure 4 In an embodiment, the step of forming a film may include: (i) placing a substrate 101a in a deposition chamber of a reactor; (ii) depositing 102, 103 one or more layers comprising hafnium, zirconium and oxygen on the substrate in the deposition chamber by thermal cycle vapor deposition, such as by thermal atomic layer deposition; after depositing the one or more layers on the substrate under the action of an electric field, (iii) placing the substrate 101b in an annealing chamber of the reactor without air interruption; (iv) annealing 105 the substrate in the annealing chamber; and repeating (i)-(iv) one or more times in one cycle to form a film.

[0104] Reference now Figure 3 and 5 In an embodiment, the step of annealing 105 the film may be performed under the effect of an electric field. If the annealing is performed on a holder, the electric field may be generated 104 in the same way as during film deposition.

[0105] If annealing 105 is performed in a separate annealing chamber of the reactor, the annealing chamber may include means for exposing the substrate to an electric field.

[0106] In an embodiment, the annealing chamber may include a housing, an annealing furnace support plate located within the housing, two electric field plates (a lower electric field plate and an upper electric field plate) arranged parallel to each other on either side of the support plate, a heating unit for heating the support plate, and a voltage controller electrically connected to one electric field plate and the other electric field plate is grounded. These connections allow an electric field to be formed within a specified distance between the lower electric field plate and the upper electric field plate.

[0107] The characteristics of the electric field may be the same as those of the electric field generated during film deposition.

[0108] Reference now Figure 6 In a second aspect, the invention relates to a thermal cycle vapor deposition system, such as a thermal atomic layer deposition system 1, comprising a reactor 2 suitable for forming 100 a film comprising hafnium, zirconium and oxygen by thermal cycle vapor deposition (such as thermal atomic layer deposition), and comprising:

[0109] an electric field generator 12 configured to generate an electric field during the formation 100 of the film; and

[0110] - A controller 14 configured to direct thermal cyclic vapor deposition, such as thermal atomic layer deposition of a film, and to operate the electric field generator 12 to generate the electric field 13 during thermal cyclic vapor deposition, such as thermal atomic layer deposition 100. When the system is capable of operating as a thermal atomic layer deposition system, it is also capable of operating as a thermal cyclic vapor deposition system.

[0111] In an embodiment, a thermal cycle vapor deposition system, such as a thermal atomic layer deposition system 1 may include:

[0112] a. Reactor 2, comprising:

[0113] a.1. Deposition chamber 3, comprising:

[0114] a.1.1. A holder 4 for a substrate 5;

[0115] a.1.2. Gas distribution system 6; and

[0116] a.1.3. A heater 7 for controlling the temperature of the holder 4;

[0117] a.2. A gas delivery system 8 for delivering reactants and precursors to a gas distribution system 6;

[0118] a.3. a vacuum system 11 for controlling the pressure within the deposition chamber 3; and

[0119] a.4. An electric field generator 12 configured to uniformly generate an electric field 13 on the holding surface of the holder 4;

[0120] b. A controller 14 configured to:

[0121] b.1. supplying heat to the holder 4 by operating the heater 7, introducing reactants and precursors to the gas distribution system 6 by operating the gas delivery system 8, and guiding a thermal cycle vapor deposition system, such as thermal atomic layer deposition; operating the vacuum system 11 to control the pressure within the deposition chamber 3, and optionally, evacuating the deposition chamber 3 in a predetermined manner during the thermal cycle vapor deposition (for example, if evacuation is performed, thermal atomic layer deposition is performed); and

[0122] b.2. Operating the electric field generator 12 to generate the electric field 13 during thermal cyclic vapor deposition (eg thermal atomic layer deposition).

[0123] exist Figure 6 (and 7, see below), the gas distribution system 6 doubles as the first conductive member. In an alternative embodiment (not shown), in addition to the gas distribution system 6, there is a separate first conductive member parallel to the holder 4, and an electric field is generated between the holder 4 and the first conductive member (rather than the gas distribution system 6).

[0124] In an embodiment, the electric field generator may be configured to generate a pulsed DC electric field uniformly on a holding surface of the holder.

[0125] In an embodiment, the reactor may include one or more deposition chambers 3 and one or more annealing chambers 3', each of these chambers 3, 3' being divided into a first compartment 31 for accommodating a substrate 5 during processing thereof and a second compartment 32 for accommodating a shared intermediate space 33 between all chambers 3, 3' for shuttling substrates 5 between adjacent chambers 3, 3', wherein the reactor 2 further includes a transfer mechanism 17 for shuttling substrates 5 between adjacent chambers 3, 3' via the shared intermediate space 33, wherein each annealing chamber 3' includes an annealing holder 4' and a second compartment 32 for controlling the annealing holder 4'. a heater 7' at a temperature of; wherein the vacuum system 11 is configured to maintain a uniform pressure across all chambers 3, 3', and wherein the controller 14 is further configured to perform a cycle one or more times, the cycle comprising: (i) placing a substrate 5 in a deposition chamber 3, (ii) thermally cyclically vapor depositing, for example, thermal atomic layer deposition of one or more layers comprising hafnium, zirconium and oxygen on the substrate 5 in the presence of an electric field, (iii) shuttling the substrate 5 to an annealing chamber 3' without air interruption, (iv) heating the substrate 5 to anneal the one or more layers to produce the film. An example of such a reactor 2 is described in detail in US2022 / 0119944A1, in particular from

[0048] to

[0065] , assuming that an electric field generator is present and configured to generate an electric field uniformly across the holding surface of the holder 4 during step (ii), and optionally an electric field uniformly across the holding surface of the annealing holder 4' during step (iv), which patent is incorporated herein by reference.

[0126] In an embodiment, the gas distribution system is a showerhead gas distribution system 6 , wherein the electric field generator 12 is configured to generate an electric field 13 between the holder 4 and the showerhead gas distribution system 6 that is uniform across a holding surface of the holder 4 .

[0127] Features of the system of the second aspect may be the same as described above with respect to the method of the first aspect.

[0128] In a third aspect, the invention relates to a computer program comprising instructions for causing the system of the second aspect to perform the steps of the method of the first aspect.

[0129] In a fourth aspect, the invention relates to a computer readable medium having stored thereon the computer program of the third aspect.

[0130] It should be understood that, although preferred embodiments, specific configurations and arrangements, and materials have been discussed herein for the device according to the present invention, various changes or modifications in form and detail may be made without departing from the scope of the present invention. Steps may be added or deleted to the described method within the scope of the present invention.

Claims

1. A method for forming a film comprising hafnium, zirconium and oxygen, the method comprising forming (100) the film by a thermal cycle vapor deposition process under the action of an electric field (13).

2. The method according to claim 1, wherein: The electric field (13) is a DC electric field (13).

3. The method according to claim 2, wherein: The DC electric field (13) is a pulsed DC electric field (13).

4. The method according to claim 3, wherein: The pulsed DC electric field (13) is pulsed at a frequency of 0.5 to 10 Hz.

5. A method according to any one of the preceding claims, wherein: The electric field (13) is uniformly distributed on and perpendicular to the deposition surface of the substrate (5) on which the film is formed.

6. The method according to claim 5, wherein: The deposition surface measures at least 300 cm 2 .

7. The method according to claim 6, wherein: The deposition surface measures at least 700 cm 2 .

8. The method according to any one of claims 5 to 7, wherein: Forming (100) the film includes: a. providing (101) a substrate (5) on a holder (4) in a chamber (3) of a reactor (2) of a thermal cycle vapor deposition system (1), the chamber (3) comprising: (i) a gas distribution system (6); (ii) a first conductive component; (iii) a holder (4) for a substrate (5), the holder (4) comprising a second conductive part (16) adapted to allow the generation of an electric field (13) between the first and second conductive parts (16), uniformly across and perpendicular to a surface of the holder (4) holding the substrate (5); b. heating the substrate (5) (102) to a temperature conducive to allowing the hafnium precursor, the zirconium precursor (10') and the oxygen source to react on the deposition surface of the substrate (5) to form a film; and c. introducing (103) a hafnium precursor, a zirconium precursor (10') and an oxygen source into the chamber (3) one or more times in a predetermined sequence via a gas distribution system (6), thereby allowing a reaction on the heated deposition surface of the substrate (5) to form a film; Therein, during step c, an electric field (13) is generated (104) which is uniformly distributed on the surface of a holder (4) holding the substrate (5) and is perpendicular thereto.

9. The method according to claim 8, wherein: The gas distribution system and the first conductive component are identical and are a showerhead gas distribution system, wherein the second conductive component (16) is adapted to allow the generation of an electric field (13) between the holder (4) and the showerhead gas distribution system (6), and wherein, during step c, an electric field (13) is generated (104) between the holder (4) and the showerhead gas distribution system (6), the electric field (13) being uniformly distributed over and perpendicular to the surface of the holder (4) holding the substrate (5).

10. The method according to claim 8 or 9, wherein: The conductive component (16) is a conductive grid (16).

11. The method according to any one of the preceding claims, further comprising the step of in-situ annealing (105) the film after its formation.

12. The method according to claim 11, wherein: The step (100) of forming the film comprises: (i) placing (101a) a substrate (5) in a deposition chamber (3) of a reactor (2); (ii) depositing (106) one or more layers comprising hafnium, zirconium and oxygen on the substrate (4) in the deposition chamber (3) by thermal cycle vapor deposition under the action of an electric field; after depositing (106) one or more layers on the substrate (4), (iii) placing (101b) the substrate in an annealing chamber (3') of the reactor (2) without air interruption; (iv) annealing (105) the substrate (4) in the annealing chamber (3'); and repeating (i)-(iv) one or more times in a cycle to form a film.

13. The method according to claim 11 or 12, wherein: A step of annealing (105) the film is performed under the effect of said electric field (13).

14. A method according to any one of the preceding claims, wherein: The thermal cyclic vapor deposition process includes at least one thermal atomic layer deposition cycle.

15. A method according to any one of the preceding claims, wherein: The thermal cycle vapor deposition process is thermal atomic layer deposition.

16. A thermal cycle vapor deposition system (1) comprising a reactor (2) adapted to form (100) a film comprising hafnium, zirconium and oxygen by thermal cycle vapor deposition, and comprising: - an electric field generator (12) configured to generate an electric field during the formation (100) of the film; as well as - a controller (14) configured to direct the thermal cyclic vapor deposition of the film and to operate the electric field generator (12) to generate the electric field (13) during the thermal cyclic vapor deposition (100).

17. The thermal cycle vapor deposition system (1) according to claim 16, comprising: a. Reactor (2), comprising: a.

1. Deposition chamber (3), comprising: a.1.

1. A holder (4) for a substrate (5); a.1.

2. Gas distribution system (6); and a.1.

3. A heater (7) for controlling the temperature of the holder (4); a.

2. a gas delivery system (8) for delivering reactants and precursors to a gas distribution system (6); a.

3. a vacuum system (11) for controlling the pressure within the deposition chamber (3); and a.

4. an electric field generator (12) configured to uniformly generate an electric field (13) on the holding surface of the holder (4); b. A controller (14) configured to: b.

1. supplying heat to the holder (4) by operating the heater (7), introducing reactants and precursors to the gas distribution system (6) by operating the gas delivery system (8), and guiding the thermal cycle vapor deposition; operating the vacuum system (11) to control the pressure in the deposition chamber (3), and evacuating the deposition chamber (3) in a predetermined manner during the thermal cycle vapor deposition; and b.

2. Operating the electric field generator (12) to generate the electric field (13) during the thermal cycle vapor deposition.

18. The thermal cycle vapor deposition system (1) according to claim 16 or 17, wherein: The electric field generator (12) is configured to generate a pulsed DC electric field (13) uniformly on a holding surface of the holder (4).

19. The thermal cycle vapor deposition system (1) according to any one of claims 16 to 18, wherein: The reactor (2) comprises one or more deposition chambers (3) and one or more annealing chambers (3'), each of these chambers (3, 3') being divided into a first compartment (31) for accommodating a substrate (5) during processing thereof and a second compartment (32) for accommodating a shared intermediate space (33) between all chambers (3, 3') for shuttling substrates (5) between adjacent chambers (3, 3'), wherein the reactor (2) further comprises a transfer mechanism (17) for shuttling substrates (5) between adjacent chambers (3, 3') via the shared intermediate space (33), wherein each annealing chamber (3') comprises an annealing holder (4') and a second compartment (32) for controlling the substrate (5) between adjacent chambers (3, 3'). a heater (7') for controlling the temperature of the annealing holder (4'); wherein the vacuum system (11) is configured to maintain a uniform pressure across all chambers (3, 3'), and wherein the controller (14) is further configured to perform a cycle one or more times, the cycle comprising: (i) placing a substrate (5) in a deposition chamber (3), (ii) thermally cyclically vapor depositing one or more layers comprising hafnium, zirconium and oxygen on the substrate (5) in the presence of an electric field, (iii) shuttling the substrate (5) to the annealing chamber (3') without air interruption, and (iv) heating the substrate (5) to anneal the one or more layers to produce the film.

20. The thermal cycle vapor deposition system (1) according to any one of claims 17 to 19, wherein: The gas distribution system (6) is a showerhead gas distribution system (6), wherein the electric field generator (12) is configured to generate an electric field (13) between the holder (4) and the showerhead gas distribution system (6) that is uniform across a holding surface of the holder (4).

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