CN117265510A - Atomic layer deposition method and atomic layer deposition system - Google Patents

Atomic layer deposition method and atomic layer deposition system Download PDF

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Publication number
CN117265510A
CN117265510A CN202311577187.7A CN202311577187A CN117265510A CN 117265510 A CN117265510 A CN 117265510A CN 202311577187 A CN202311577187 A CN 202311577187A CN 117265510 A CN117265510 A CN 117265510A
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target
proportion
proportion group
order
target element
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CN117265510B (en
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邵大立
史皓然
齐彪
李宇晗
陆淋康
刘子婵
马敬忠
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Hangzhou Xingyuanchi Semiconductor Co.,Ltd.
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Shanghai Xingyuanchi Semiconductor Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/52—Controlling or regulating the coating process
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Engineering & Computer Science (AREA)
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Abstract

The present disclosure relates to the field of material deposition processes, and in particular, to an atomic layer deposition method and an atomic layer deposition system. The atomic layer deposition method comprises the following steps: determining a metal element in a metal oxide layer to be deposited as a target element; obtaining a target proportion group of the corresponding component proportion of each target element; acquiring a first reference proportion group and first-order process parameters corresponding to the first reference proportion group according to the target proportion group, wherein the first reference proportion group is a first-order historical proportion group closest to the target proportion group in a plurality of first-order historical proportion group data of different component proportions corresponding to each target element; determining a second-order technological parameter according to the proportion difference value corresponding to each target element in the target proportion group and the first reference proportion group; in response to the first order process parameter and the second order process parameter, a metal oxide layer is deposited, the metal oxide layer comprising a plurality of metal elements. The atomic layer deposition method can obtain the metal oxide layer with the required components, and realizes the precise control of the components of the metal oxide layer.

Description

Atomic layer deposition method and atomic layer deposition system
Technical Field
The present disclosure relates to the field of material deposition processes, and in particular, to an atomic layer deposition method and an atomic layer deposition system.
Background
The atomic layer deposition (Atomic layer deposition, ALD) process is a chemical vapor deposition process based on surface self-saturation reactions, which has an irreplaceable position in the field of semiconductor manufacturing. In the atomic layer deposition process, the gas phase precursor pulse is introduced into the deposition cavity and then is chemically adsorbed on the surface of the substrate, and chemical reaction is carried out on the surface of the substrate, so that the monoatomic film is deposited on the surface of the substrate. The atomic layer deposition process can plate substances on the surface of the substrate layer by layer in a single atomic film mode, so that the thickness of the film can be accurately controlled.
For a metal oxide containing a plurality of metal elements, the content of each metal element determines the performance of the metal oxide. The requirements of different application fields on the performance of the metal oxide are different, so that the different application fields have different requirements on the components of the metal oxide, and the components of the metal oxide need to be precisely controlled so as to meet the requirements of different fields on the performance of the metal oxide.
Disclosure of Invention
Based on this, the present disclosure provides an atomic layer deposition method and an atomic layer deposition system for precise control of the composition of metal oxides.
In a first aspect, the present disclosure provides an atomic layer deposition method for depositing a metal oxide layer, the metal oxide layer including a plurality of metal elements, the atomic layer deposition method comprising: determining the metal element in the metal oxide layer to be deposited as a target element; obtaining a target proportion group of the corresponding component proportion of each target element; acquiring a first reference proportion group and first-order process parameters corresponding to the first reference proportion group according to the target proportion group, wherein the first reference proportion group is a first-order historical proportion group closest to the target proportion group in a plurality of first-order historical proportion group data of different component proportions corresponding to each target element; determining a second-order technological parameter according to the proportion difference value corresponding to each target element in the target proportion group and the first reference proportion group; the metal oxide layer is deposited in response to the first order process parameter and the second order process parameter.
According to the atomic layer deposition method, first reference proportion groups and first-order process parameters corresponding to the first reference proportion groups are obtained according to target proportion groups of metal oxide layers to be deposited, second-order process parameters are determined according to proportion differences corresponding to target elements in the target proportion groups and the first reference proportion groups, so that specific process parameters required for depositing the metal oxide layers are determined, deposition of the metal oxide layers is carried out according to the obtained specific process parameters, metal oxide layers with required components can be obtained, and accurate control of the metal oxide layer components is achieved.
In some embodiments, the step of depositing a metal oxide layer comprises: performing a deposition process in a plurality of main cycles; wherein any one of the main cycles comprises: performing deposition according to the generation sequence of the oxide corresponding to each target element and the target number of sub-cycles for each target element in sequence; the first-order process parameters comprise the cycle times of the sub-cycles corresponding to the target elements, and the second-order process parameters comprise the pulse width of the precursor gas corresponding to the target elements.
In some embodiments, in the process parameters corresponding to different first-order history proportion groups, pulse widths of precursor supplies corresponding to the same target element are the same, and cycle numbers of the sub-cycles corresponding to the same target element are different.
In some embodiments, the step of determining the second-order process parameter according to the ratio difference value corresponding to each target element in the target ratio set and the first reference ratio set includes: and determining the regulation direction and regulation range of each target element corresponding to the second-order technological parameter according to the proportion difference value corresponding to each target element in the target proportion group and the first reference proportion group.
In some embodiments, the atomic layer deposition method further comprises: after determining the regulation direction and regulation range of each target element corresponding to the second-order process parameter, acquiring a second reference proportion group and the second-order process parameter corresponding to the second reference proportion group according to the target proportion group; the second reference proportion group is a second-order history proportion group which is the same as the target proportion group in a plurality of second-order history proportion group data of different component proportions corresponding to each target element.
In some embodiments, in the process parameters corresponding to different second-order history proportion groups, the number of cycles of the sub-cycles corresponding to the same target element is the same, and pulse widths of the precursor gas corresponding to the same target element are different.
In some embodiments, at least one of the pulse widths of the respective target element corresponding precursor supplies is incremented by a preset time interval, the preset time interval being 10ms-20ms.
In some embodiments, the target element is three kinds; the step of obtaining a first reference proportion group according to the target proportion group comprises the following steps: sequentially linking coordinate axes of the corresponding component proportions of each target element into a first triangular coordinate system; marking the first-order historical proportion group data of the corresponding component proportion of each target element in the first triangular coordinate system according to a first identification; marking the target proportion group of the corresponding component proportion of each target element in the first triangular coordinate system according to a second identifier; and determining a first mark closest to the second mark in the first triangular coordinate system, and taking a first-order history proportion group corresponding to the first mark as the first reference proportion group.
In some embodiments, the target element is three kinds; the step of obtaining a second reference proportion group according to the target proportion group comprises the following steps: sequentially linking coordinate axes of the target elements corresponding to the component proportions into a second triangular coordinate system; marking the second-order historical proportion group data of the corresponding component proportion of each target element in the second triangular coordinate system according to a second identifier; marking the target proportion group of the corresponding component proportion of each target element in the second triangular coordinate system according to a second identifier; and determining a second mark closest to the second mark in the second triangular coordinate system, and taking a second-order history proportion group corresponding to the second mark as the second reference proportion group.
In some embodiments, the metal oxide layer is a metal oxide semiconductor layer.
In some embodiments, the material of the metal oxide semiconductor layer comprises indium gallium zinc oxide.
In some embodiments, the precursor gases for depositing the indium gallium zinc oxide include an indium source gas, a gallium source gas, and a zinc source gas; the pulse width of the indium source gas is 0.1s-2s, the pulse width of the gallium source gas is 20ms-200ms, and the pulse width of the zinc source gas is 20ms-200ms.
In some embodiments, the atomic layer deposition method further comprises: acquiring a growth rate curve of the oxide corresponding to each target element at different temperatures; and determining a target growth temperature of the oxide corresponding to each target element according to each growth rate curve, wherein the slope of the growth rate curve of the oxide corresponding to each target element is smaller at the target growth temperature. Even if the temperature of the deposition chamber fluctuates during the growth of the metal oxide, the target growth temperature can enable the metal oxide to grow at a relatively stable growth rate, so that the components of the deposited metal oxide layer are target components, and precise control of the components of the metal oxide layer is ensured.
In some embodiments, the target growth temperature of each of the target elements corresponding to an oxide is the same. After the deposition of one oxide atomic layer is completed, the temperature of the deposition chamber does not need to be regulated to be matched with the deposition temperature of the next oxide atomic layer, so that the operation procedures in the atomic layer deposition process are reduced, the waiting time of temperature rise and temperature reduction is shortened, and the mass production efficiency is improved.
In a second aspect, the present application provides an atomic layer deposition system comprising: a deposition chamber for depositing a metal oxide layer on a substrate, the metal oxide layer comprising a plurality of metal elements; the parameter determining module is used for determining the metal element in the metal oxide layer to be deposited as a target element, obtaining a target proportion group corresponding to the component proportion of each target element, obtaining a first reference proportion group and first-order process parameters corresponding to the first reference proportion group according to the target proportion group, and determining second-order process parameters according to the proportion difference value corresponding to each target element in the target proportion group and the first reference proportion group; the storage module is connected with the parameter determination module and is used for storing first-order historical proportion group data and process parameters of the corresponding component proportions of each target element; the gas supply device is connected with the deposition chamber and is used for supplying reaction gas to the deposition chamber, and the reaction gas at least comprises precursors corresponding to each target element; the control module is connected with the parameter determination module and the air supply device and is configured to: the gas supply device is controlled to supply a reactive gas to the deposition chamber in response to the first order process parameter and the second order process parameter.
In some embodiments, the atomic layer deposition system further comprises: one or more serially connected preheating chambers located at a substrate transfer front side of the deposition chamber for preheating the temperature of the substrate. The arrangement of the preheating chamber can shorten the time for the substrate to reach the deposition temperature after the substrate enters the deposition chamber, thereby being beneficial to improving the deposition efficiency; meanwhile, in the process of depositing one substrate by the deposition chamber, the next substrate to be deposited can be preheated by the preheating chamber, so that continuous production is facilitated, and the mass production efficiency is improved.
Drawings
In order to more clearly illustrate the technical solutions of embodiments or conventional techniques of the present application, the drawings required for the descriptions of the embodiments or conventional techniques will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is a flow chart of an atomic layer deposition method provided in one embodiment;
FIG. 2 is a schematic diagram of a first triangular coordinate system according to an embodiment;
FIG. 3 is In 2 O 3 、Ga 2 O 3 And a growth rate profile of ZnO at different temperatures;
FIG. 4 is a schematic diagram of an atomic layer deposition system according to one embodiment;
FIG. 5 is a flow chart of a process for depositing an IGZO film according to one embodiment;
FIG. 6 is a schematic diagram of pulse timing of a main cycle and each sub-cycle during IGZO deposition according to an embodiment;
reference numerals illustrate:
1-a deposition chamber; 2-an inert gas output module; a 3-ozone output module; 4-a precursor output module; a 5-pulse valve module; 6-preheating the chamber; 7-a first transition chamber; 8-a second transition chamber; 9-a vacuum pump; 10-a first temperature control member; 11-an oxygen output module; 12-a plasma generator; 13-a first transfer device; 14-a second conveyor; 15-a second temperature control member; 16-a pressure control member; 17-tail gas treatment device.
Detailed Description
In order to facilitate an understanding of the present application, a more complete description of the present application will now be provided with reference to the relevant figures. Examples of the present application are given in the accompanying drawings. This application may, however, be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
As described in the background art, in order to meet the requirements of different fields for the performance of metal oxides, precise control of the composition of metal oxides containing a plurality of metal elements is required.
For example, indium gallium zinc oxide (Indium Gallium Zinc Oxide, IGZO) is formed of In 2 O 3 、Ga 2 O 3 And ZnO three compounds according to different proportions. Research shows that In 2 O 3 In 3+ The 5S electron orbit at the microscopic level can greatly improve the transmission speed of carriers and Ga 2 O 3 Has extremely strong ionic bond, can effectively inhibit the generation of O vacancy, and Zn in ZnO 2+ A tetrahedral structure with a very stable structure can be formed, thereby enabling IGZO to form a stable amorphous structure. IGZO also has a series of advantages of low off-state current, wide band gap, good stability and the like, so that the IGZO has wide application prospects in various fields such as Thin Film Transistors (TFTs), flexible electronic devices, photoelectric sensors and the like. The different application fields have different requirements on the proportion of In, ga and Zn In the IGZO film. When IGZO is used for a channel material of a thin film transistor, increasing the content of gallium oxide can reduce off-state current of the thin film transistor and reduce electric leakage, but can cause a decrease in response speed of the thin film transistor, so that it is necessary to find a balance point to optimize the performance of the thin film transistor. When the IGZO is applied to a high-definition display, the content of zinc element in the IGZO is not more than 71.4%, so that the IGZO film has better visible light transmittance, and the full-definition or even ultra-high-definition display can be obtained. Accurate control of the composition of the IGZO film during deposition is advantageous in obtaining an IGZO film having an optimal ratio. Therefore, how to precisely control the composition of IGZO thin films during deposition is one research direction that industry is continually striving to explore.
Based on this, in a first aspect, referring to fig. 1, the present application provides an atomic layer deposition method for depositing a metal oxide layer, the metal oxide layer containing a plurality of metal elements, the atomic layer deposition method of the present application comprising the steps of:
step S1, determining a metal element in a metal oxide layer to be deposited as a target element;
s2, obtaining a target proportion group of the corresponding component proportion of each target element;
step S3, acquiring a first reference proportion group and first-order process parameters corresponding to the first reference proportion group according to the target proportion group, wherein the first reference proportion group is a first-order historical proportion group closest to the target proportion group in a plurality of first-order historical proportion group data of different component proportions corresponding to each target element;
s4, determining second-order technological parameters according to the proportion difference value corresponding to each target element in the target proportion group and the first reference proportion group;
and step S5, a metal oxide layer is deposited in response to the first-order process parameter and the second-order process parameter.
According to the atomic layer deposition method, the first reference proportion group and the first-order process parameters corresponding to the first reference proportion group are firstly obtained according to the target proportion group of the metal oxide layer to be deposited, the second-order process parameters are then determined according to the proportion differences corresponding to all target elements in the target proportion group and the first reference proportion group, so that the specific process parameters required for depositing the metal oxide layer are determined, the metal oxide layer with the required components can be obtained by depositing the metal oxide layer according to the obtained specific process parameters, and the accurate control of the metal oxide layer components is realized.
It can be understood that: the first order process parameters and the second order process parameters are different and form a process parameter set of the metal oxide layer together. Before actual production, respectively depositing a metal oxide layer by using different process parameter groups, wherein the different process parameter groups have the same second-order process parameters and different first-order process parameters, carrying out component analysis on the deposited metal oxide layer, forming a first-order sub-database by using a plurality of process parameter group data and a plurality of metal oxide layer group data, and associating the process parameter group data in the first-order sub-database with corresponding metal oxide layer group data; in actual production, component data closest to a target component of the metal oxide layer to be deposited is found in the first-order sub-database and is recorded as reference component data, and first-order process parameters in a process parameter set associated with the reference component data are first-order process parameters of the metal oxide layer to be deposited; after the first-order process parameters are determined, second-order process parameters of the target components of the metal oxide layer to be deposited are further determined according to the difference value between the reference component data and the target components; after the first-order process parameters and the second-order process parameters are obtained, the metal oxide layer to be deposited can be deposited.
In some embodiments, the step of depositing the metal oxide layer includes performing the deposition process in a plurality of main cycles, wherein any one of the main cycles includes performing the deposition in a target number of sub-cycles for each target element in turn according to a sequence of formation of the corresponding oxide for each target element. In other words, the deposition process of the metal oxide comprises a plurality of main cycles which are sequentially performed, each main cycle comprising n which are sequentially performed 1 First sub-cycle, n 2 A second sub-cycle to n j A j-th sub-cycle, each sub-cycle being used for forming an oxide atomic layer of a single metal element, the metal elements of the oxide atomic layers formed from the first sub-cycle to the j-th sub-cycle being different, the number of metal elements in the metal oxide being j, j being an integer greater than or equal to 2, n 1 To n j Are integers greater than or equal to 1, and each sub-cycle comprises the following steps performed in sequence: introducing a precursor gas containing a single metal element into a deposition chamber, purging the deposition chamber with an inert gas, introducing the deposition chamber with an oxidizing gas, purging the deposition chamber with an inert gas, wherein the precursor gas introduced from the first sub-cycle to the j sub-cycle has different metal elements, and n is the number of the main cycles 1 To n j The amount of precursor and the time of passage of the precursor in the first to j-th sub-cycles determine the composition of the metal oxide layer. The first-order process parameters comprise the circulation times of the subcycles corresponding to each target element, namely the numbers of the first subcycles to the j-th subcycles in the main cycle, and the second-order process parameters comprise eachThe target element corresponds to the pulse width of the precursor gas supply, i.e., the time of the precursor gas introduction in the first to the j-th sub-cycles of the main cycle. That is, step S3 is performed to obtain the number of sub-cycles corresponding to each target element, and step S4 is performed to obtain the pulse width of the precursor gas corresponding to each target element. The cycle times of the sub-cycle are mainly used for coarse adjustment of the components of the metal oxide, and the pulse width of the precursor gas supply is mainly used for accurate adjustment and control of the components of the metal oxide, so that the cycle times of the sub-cycle are preferentially determined.
In some embodiments, in step S3, in the process parameters corresponding to different first-order history proportion groups, pulse widths of the precursor supplies corresponding to the same target element are the same, and cycle numbers of sub-cycles corresponding to the same target element are different. In other words, in different process parameter sets of the first-order sub-database, the same precursor gas is introduced for the same time, and the ratios of the numbers of the first sub-cycle to the j-th sub-cycle are different. On the basis, the step S3 can obtain the cycle number of the sub-cycle corresponding to each target element, and the subsequent step S4 is used to obtain the pulse width of the precursor gas corresponding to each target element.
In some embodiments, in step S4, the step of determining the second-order process parameter according to the ratio differences corresponding to the target elements in the target ratio set and the first reference ratio set includes: and determining the regulation and control direction and regulation and control range of the second-order technological parameters corresponding to each target element according to the proportion difference value corresponding to each target element in the target proportion group and the first reference proportion group. The regulation and control range refers to whether the second-order technological parameters corresponding to each target element are increased or reduced on the basis of the second-order technological parameters corresponding to the reference proportion group, for example, the pulse width of the precursor gas corresponding to each target element is increased or reduced; the regulation and control range refers to the range of the second-order technological parameter corresponding to each target element to be increased or reduced based on the second-order technological parameter corresponding to the reference proportion group.
In some preferred embodiments, the atomic layer deposition method further comprises: after determining the regulation direction and regulation range of the second-order process parameters corresponding to each target element, acquiring a second reference proportion group and the second-order process parameters corresponding to the second reference proportion group according to the target proportion group; the second reference proportion group is a second-order history proportion group which is the same as the target proportion group in a plurality of second-order history proportion group data of which each target element corresponds to different component proportions.
It can be understood that: before actual production, besides the first-order sub-database, a plurality of second-order sub-databases are also required to be constructed, the process parameter group data in the same second-order sub-database has the same first-order process parameters and different second-order process parameters, the process parameter group data in the second-order sub-database are associated with the component data of the metal oxide layer prepared by adopting the corresponding process parameter group, the first-order process parameters of the different second-order sub-databases are different, and the construction method of the second-order sub-database is the same as that of the first-order sub-database. When in actual production, after the first-order process parameters are determined, locking a second-order sub-database according to the first-order process parameters, indexing the metal oxide layer component data which are the same as the target component of the metal oxide layer to be deposited in the second-order sub-database, wherein the second-order process parameters in the process parameter group which are related to the metal oxide layer component data are the second-order process parameters of the metal oxide layer to be deposited. It should be noted that if the first-order sub-database and the second-order sub-databases are not respectively constructed, but a huge database is constructed, and the databases are stored with the data in the first-order sub-database and the second-order sub-databases and are not classified, then the process parameter sets of the target metal oxide layer to be deposited need to be indexed in the huge database, so that the efficiency is low; by constructing the first-order sub-database and the second-order sub-databases, the first-order process parameters and the second-order process parameters can be rapidly indexed, and the efficiency is high, namely, the history proportion group data is divided into the first-order history proportion group data and the second-order history proportion group data, the first-order process parameters and the second-order process parameters can be rapidly indexed, and the efficiency is high.
In some embodiments, in the process parameters corresponding to different second-order history proportion groups, the cycle times of sub-cycles corresponding to the same target element are the same, and pulse widths of precursor gas corresponding to the same target element are different. In other words, in the different process parameter sets of the second sub-database, the ratio of the numbers of the first sub-cycle to the j sub-cycle is the same, and the same precursor gas is introduced at different times. On this basis, step S4 can obtain the pulse width of the precursor gas supply corresponding to each target element.
In some embodiments, each target element is incremented by a preset time interval corresponding to at least one of the pulse widths of the precursor supplies, which may be 10ms-20ms, e.g., 10ms, 11ms, 12ms, 13ms, 14ms, 15ms, 16ms, 17ms, 18ms, 19ms, or 20ms. The preset time interval influences the number and the density of the process parameter groups in the second-order sub-database, and the smaller the preset time interval is, the smaller the density of the process parameter groups is, the larger the number is, so that the more metal oxide components can be covered, and the atomic layer deposition method can realize accurate control of the components on the more metal oxides.
As a specific example, the kinds of target elements are three; the step of obtaining a first reference proportion group according to the target proportion group comprises the following steps: sequentially linking coordinate axes of the corresponding component proportions of each target element into a first triangular coordinate system; marking the first-order historical proportion group data of the corresponding component proportion of each target element in a first triangular coordinate system according to a first identifier; marking a target proportion group of the corresponding component proportion of each target element in a first triangular coordinate system according to a second identification; and determining a first mark closest to the second mark in the first triangular coordinate system, and taking the first-order history proportion group corresponding to the first mark as a first reference proportion group.
As a specific example, the kinds of target elements are three; the step of obtaining a second reference proportion set according to the target proportion set comprises the following steps: sequentially linking coordinate axes of the corresponding component proportions of each target element into a second triangular coordinate system; marking the second-order historical proportion group data of the corresponding component proportions of each target element in a second triangular coordinate system according to a second identifier; marking a target proportion group of the corresponding component proportion of each target element in a second triangular coordinate system according to a second identification; and determining a second mark closest to the second mark in the second triangular coordinate system, and taking the second-order history proportion group corresponding to the second mark as a second reference proportion group.
In other words, the step of obtaining the first reference proportion set and the second reference proportion set is:
establishing a coordinate system, wherein each coordinate axis respectively represents the content of a single metal element in the metal oxide, and the number of the coordinate axes is the same as that of the metal elements in the inorganic compound; the coordinate system comprises a first order coordinate system and a plurality of second order coordinate systems,
before actual production, converting the metal oxide components in the first-order sub-database into coordinates and marking the coordinates in a first-order coordinate system, converting the metal oxide components in the second-order sub-database into coordinates and marking the coordinates in a corresponding second-order coordinate system, wherein each coordinate point in the first-order coordinate system and the second-order coordinate system corresponds to a set of process parameters for depositing corresponding metal oxide;
Converting the components of the metal oxide layer to be deposited into target coordinate points, marking the target coordinate points in a first-order coordinate system, selecting the coordinate points with the minimum distance from the target coordinate points, wherein the coordinate points correspond to a first reference proportion group, and the first-order process parameters in the process parameter group corresponding to the coordinate points are the first-order process parameters of the metal oxide layer to be deposited;
indexing a corresponding second-order coordinate system according to the first-order process parameters, indexing a coordinate point corresponding to a target coordinate point in the second-order coordinate system, wherein the coordinate point corresponds to a second reference proportion group, and the second-order process parameters in the process parameter group corresponding to the coordinate point are the second-order process parameters of the metal oxide layer to be deposited.
Specifically, the metal oxide layer may be a metal oxide semiconductor layer, and a material of the metal oxide semiconductor layer includes, but is not limited to, indium Gallium Zinc Oxide (IGZO). Precursors for depositing indium gallium zinc oxide include an indium source, a gallium source, and a zinc source, the indium source including (CH 3 ) 2 In(CH 2 ) 3 N(CH 3 ) 2 (DADI) the gallium source comprises Ga (CH) 3 ) 3 (TMGa), the zinc source comprises (C 2 H 5 ) 2 Zn (DEZ), the indium source, the gallium source and the zinc source are all in liquid state at normal temperatureThe method comprises the steps of carrying out a first treatment on the surface of the The pulse width of the indium source gas may range from 0.1s to 2s, the pulse width of the gallium source gas may range from 20ms to 200ms, and the pulse width of the zinc source gas may range from 20ms to 200ms. When a first-order sub-database is constructed, the pulse widths of the three precursor gases are respectively positioned in the corresponding pulse width ranges; in the second sub-database, the pulse widths of the three precursor gases are adjusted within the corresponding pulse width ranges and are respectively increased at preset time intervals.
By way of example, fig. 2 shows a first order coordinate system (i.e., a first triangular coordinate system) in which the metal oxide composition in the first order sub-database is converted into coordinates and marked prior to actual production, and fig. 2 shows only a portion of the coordinate points such as A, B, C, each of which is associated with the formation of a corresponding metal oxide composition.
If the composition of the IGZO film to be deposited is In 0.53 Ga 0.33 Zn 0.14 O, namely 53%, 33% and 14% of the target percentages of three atoms of In, ga and Zn In the IGZO film respectively, and the target coordinate point is (0.53,0.33,0.14);
the atomic layer deposition system automatically marks the target coordinate point in a first-order coordinate system (star position), compares the target coordinate point with the A, B, C coordinate points in the first-order coordinate system, and obtains that the distance between the target coordinate point and the coordinate point A is shortest; when an IGZO film corresponding to the coordinate point A is deposited by adopting an atomic layer deposition process, each main cycle comprises m 1 In number of 2 O 3 Sub-cycle, m 2 Ga (P) atoms 2 O 3 Sub-cycle sum m 3 The ZnO sub-cycle is determined, so that m can be adopted when the IGZO film required for deposition 1 In number of 2 O 3 Sub-cycle, m 2 Ga (P) atoms 2 O 3 Sub-cycle sum m 3 The ZnO sub-cycle is carried out, and the first-order technological parameters are determined;
determining a second-order coordinate system according to the first-order process parameters, wherein the second-order coordinate system is similar to the first-order coordinate system, is a triangular coordinate system, and is different from the first-order coordinate system only in coordinate points in the second-order coordinate system, but contains coordinate points A; marking the target coordinate point at two In corresponding to coordinate point overlapping with target coordinate point In order coordinate system 2 O 3 Sub-cycle, ga 2 O 3 The pulse width of the subcycle and the ZnO subcycle is the second-order technological parameter of the IGZO film required by deposition.
It should be noted that if the composition of the metal oxide layer to be deposited has an acceptable error range, the target coordinate point of the metal oxide layer to be deposited in the second-order coordinate system may define a region, and the coordinate point with the smallest error is selected from the region to determine the second-order process parameter.
In some embodiments, the atomic layer deposition method further comprises: acquiring growth rate curves of oxides corresponding to each target element at different temperatures; and determining the target growth temperature of the oxide corresponding to each target element according to each growth rate curve, wherein the slope of the growth rate curve of the oxide corresponding to the target element at the target growth temperature is smaller. Even if the temperature of the deposition chamber fluctuates during the growth of the metal oxide, the target growth temperature can enable the metal oxide to grow at a relatively stable growth rate, so that the components of the deposited metal oxide layer are target components, and precise control of the components of the metal oxide layer is ensured. FIG. 3 shows In 2 O 3 、Ga 2 O 3 And growth rate curves of ZnO at different temperatures.
Preferably, the target growth temperature of the oxide corresponding to each target element is the same. After the deposition of one oxide atomic layer is completed, the temperature of the deposition chamber does not need to be regulated to be matched with the deposition temperature of the next oxide atomic layer, so that the operation procedures in the atomic layer deposition process are reduced, the waiting time of temperature rise and temperature reduction is shortened, and the mass production efficiency is improved. With continued reference to FIG. 3, in 2 O 3 、Ga 2 O 3 And the target growth temperature of ZnO is the temperature range indicated by the gray area in FIG. 3, specifically, the temperature of the deposition chamber is controlled within 140-160 ℃ in the process of depositing the indium gallium zinc oxide layer.
In a second aspect, referring to fig. 4, the present application further provides an atomic layer deposition system, comprising:
a deposition chamber 1 for depositing a metal oxide layer on a substrate, the metal oxide layer containing a plurality of metal elements;
the parameter determining module (not shown) is used for determining that metal elements in the metal oxide layer to be deposited are target elements, obtaining target proportion groups corresponding to component proportions of the target elements, obtaining a first reference proportion group and first-order process parameters corresponding to the first reference proportion group according to the target proportion groups, and determining second-order process parameters according to proportion differences corresponding to the target elements in the target proportion groups and the first reference proportion groups;
The storage module (not shown) is connected with the parameter determination module and is used for storing first-order historical proportion group data and process parameters of the corresponding component proportions of each target element;
the gas supply device is connected with the deposition chamber 1 and is used for supplying reaction gas to the deposition chamber 1, wherein the reaction gas at least comprises precursors corresponding to all target elements;
a control module (not shown), connected to the parameter determination module and the air supply device, configured to: the gas supply means is controlled to supply the reaction gas to the deposition chamber 1 in response to the first-order process parameter and the second-order process parameter.
Specifically, with continued reference to fig. 4, the gas supply device includes a plurality of gas output modules, a plurality of gas pipelines and a plurality of pulse valves, the plurality of pulse valves form a pulse valve module 5, the deposition chamber 1 and the plurality of gas output modules are respectively communicated through the gas pipelines, the plurality of pulse valves are respectively arranged on the gas pipelines connected with different gas output modules, the control module is electrically connected with the plurality of pulse valves, and the control module is suitable for controlling the switching of the plurality of pulse valves so as to respectively control the gas from different gas output modules to enter the deposition chamber 1. The gas output module comprises an inert gas output module 2, an ozone output module 3 and a plurality of precursor output modules 4, wherein the precursor output modules 4 comprise a precursor storage, a heating device and the like, and the inert gas output module 2 is also communicated with the precursor storage.
In some embodiments, with continued reference to fig. 4, the atomic layer deposition system further includes one or more preheating chambers 6 in series, one preheating chamber 6 being shown in fig. 4, located on the substrate transfer front side of the deposition chamber 1 for preheating the temperature of the substrate. Specifically, a second heating element (not shown) is disposed in the preheating chamber 6, and the temperature of the preheating chamber 6 is less than or equal to the deposition temperature of the metal oxide in the deposition chamber 1. In actual mass production, it tends to take a lot of time to raise the temperature of the substrate to the deposition temperature of the metal oxide. The arrangement of the preheating chamber 6 can shorten the time for the substrate to reach the deposition temperature after the substrate enters the deposition chamber 1, thereby being beneficial to improving the deposition efficiency; meanwhile, in the process of depositing one substrate by the deposition chamber 1, the preheating chamber 6 can preheat the next substrate to be deposited, which is beneficial to realizing continuous production, thereby improving the mass production efficiency. The production efficiency of the atomic layer deposition system is maximally improved when the time required for the preheating chamber 6 to raise the temperature of the substrate to the deposition temperature is equal to the deposition time of the substrate in the deposition chamber 1. When the thickness of the actually produced metal oxide layer is thin so that the deposition time is short, optimization of the production efficiency can be achieved by connecting a plurality of preheating chambers 6 in series.
In some embodiments, with continued reference to fig. 4, the atomic layer deposition system further includes:
a first transition chamber 7, the first transition chamber 7 being located at a side of the preheating chamber 6, the first transition chamber 7 being adapted to communicate with the preheating chamber 6;
a second transition chamber 8, the second transition chamber 8 being located at a side of the deposition chamber 1, the second transition chamber 8 being adapted to communicate with the deposition chamber 1;
the vacuum pump 9, the vacuum pump 9 is suitable for vacuumizing the deposition chamber 1, the preheating chamber 6, the first transition chamber 7 and the second transition chamber 8, so that the vacuum degree of the deposition chamber 1 reaches the vacuum degree required by depositing the metal oxide, and the vacuum degree of the preheating chamber 6, the first transition chamber 7 and the second transition chamber 8 is smaller than or equal to the vacuum degree required by depositing the metal oxide;
a transfer member (not shown) adapted to transfer the substrate from the first transition chamber 7 to the preheating chamber 6, from the preheating chamber 6 to the deposition chamber 1, and from the deposition chamber 1 to the second transition chamber 8.
In the actual deposition process, after the substrate is transferred to the deposition chamber, the air pressure in the deposition chamber needs to be reduced from the atmospheric pressure to the air pressure required for depositing the metal oxide, and after the deposition of the metal oxide is completed on the surface of the substrate, the air pressure in the deposition chamber needs to be increased to the atmospheric pressure to transfer the substrate to the outside, which consumes a lot of time. The first transition cavity 7 is pre-vacuumized after the substrate enters the first transition cavity 7, so that the vacuumizing time after the substrate enters the deposition cavity 1 is reduced; the second transition chamber 8 is vacuumized in the process of depositing the substrate, so that the substrate can be directly transferred to the second transition chamber 8 after being deposited, after the valve between the deposition chamber 1 and the second transition chamber 8 is closed, the deposition chamber 1 can perform the deposition work of the next substrate, and the second transition chamber 8 is inflated to enable the internal air pressure value to reach the atmospheric pressure so as to transfer the deposited substrate to the outside. That is, the arrangement of the first transition cavity 7 and the second transition cavity 8 shortens the time for exhausting and inflating the deposition cavity 1, thereby shortening the time of the substrate in the deposition cavity 1, being beneficial to improving the deposition efficiency, improving the production continuity and further improving the mass production efficiency. During deposition, the vacuum level of the preheating chamber 6 is substantially constant, and after the first transition chamber 7 is evacuated, the vacuum level of the first transition chamber 7 is substantially equal to the vacuum level of the preheating chamber 6.
In some embodiments, with continued reference to fig. 4, the atomic layer deposition system further includes a first heating element disposed on an outer surface of the gas line to heat the gas in the gas line, the first heating element having a temperature less than or equal to a deposition temperature of the metal oxide. On one hand, the method can avoid the precursor gas from condensing and remaining on the inner wall of the gas pipeline in the transmission process, on the other hand, the time for the precursor gas to reach the metal oxide deposition temperature in the deposition chamber 1 is reduced, the deposition efficiency is improved, and meanwhile, the rapid temperature reduction of the deposition chamber 1 caused by the fact that inert gas and ozone with lower temperature enter the deposition chamber 1 is avoided. Specifically, the temperature of the gas pipeline for conveying inert gas and ozone is controlled below 150 ℃.
Correspondingly, the atomic layer deposition system further comprises a first temperature control member 10, wherein the first temperature control member 10 is electrically connected with the first heating member, and the temperature control member is suitable for controlling the temperature of the first heating member. The first heating element may be a pipeline heating belt.
As a preferred embodiment, each gas pipeline connected with the gas output module comprises a first pipeline section and a second pipeline section which are mutually communicated, the first pipeline section and the second pipeline section are respectively positioned at two sides of the pulse valve, the first pipeline section is communicated with the gas output module, the second pipeline section is communicated with the deposition chamber, and the temperature of the second pipeline section is higher than that of the first pipeline section. The temperature of the gas from the gas output module is gradually increased after the gas enters the gas pipeline, so that the flow stability of the gas in the transmission process is improved. Illustratively, the temperature difference between the second stage conduit and the first stage conduit may range from 10 ℃ to 50 ℃, such as 10 ℃, 20 ℃, 30 ℃, 40 ℃, or 50 ℃.
In some embodiments, with continued reference to fig. 4, the atomic layer deposition system further comprises an oxygen output module 11 and a plasma generator 12, the plasma generator 12 having an input in communication with the oxygen output module 11 and an output in communication with the deposition chamber 1, the plasma generator 12 being adapted to generate and transmit an oxygen plasma to the deposition chamber 1. The atomic layer deposition system can select an oxidation mode according to the requirement, ozone can be introduced into the deposition chamber 1 through the ozone output module 3, and oxygen plasma can be introduced into the deposition chamber 1 through the oxygen output module 11 and the plasma generator 12, so that the flexibility of the atomic layer deposition system is improved.
Further, with continued reference to fig. 4, the atomic layer deposition system further includes:
a first transfer means 13 located at a side of the first transition chamber 7 for transferring the substrate to be deposited to the side passing through the first transition chamber 7;
a second transfer device 14 located at a side of the second transition chamber 8 for transferring the substrate on which the metal oxide layer has been deposited into a subsequent system;
a third heating member (not shown) located in the deposition chamber 1 for heating the deposition chamber 1 to bring the deposition chamber 1 to a deposition temperature of the metal oxide;
A second temperature control member 15 electrically connected to the third heating member in the deposition chamber 1 for controlling the temperature in the deposition chamber 1;
a control part 16 for controlling the vacuum degree of the deposition chamber 1;
the tail gas treatment device 17 comprises an input end and an output end, wherein the input end is communicated with the deposition chamber 1, the precursor output module 4, the ozone output module 3 and the inert gas output module 2, and the output end is communicated with the vacuum pump 9.
The following exemplary operation of an atomic layer deposition system is described in full:
(1) The first gate valve between the first transition chamber 7 and the first transfer device 13 is opened, and the substrate is transferred from the first transfer device 13 to the first transition chamber 7 through the transfer member, and the air pressures of the first transition chamber 7 and the first transfer device 13 are 1 atmosphere.
(2) When the substrate completely enters the first transition cavity 7, the first gate valve is closed, and the vacuum pump 9 vacuumizes the first transition cavity 7 until the air pressure in the first transition cavity 7 is reduced to be equal to the air pressure in the preheating cavity 6.
(3) The second gate valve between the first transition chamber 7 and the preheating chamber 6 is opened, the substrate enters the preheating chamber 6 from the first transition chamber 7 through the conveying member, then the second gate valve is closed, and the second heating member in the preheating chamber 6 preheats the substrate so that the temperature of the substrate is close to or even equal to the deposition temperature of the metal oxide.
(4) A third gate valve between the preheating chamber 6 and the deposition chamber 1 is opened, the substrate is transferred from the preheating chamber 6 to the deposition chamber 1 through the transfer member, and then the third gate valve is closed; the pressure and temperature of the deposition chamber 1 are controlled by the pressure control member 16 and the second temperature control member 15, respectively, until the pressure and temperature required for the deposition of the metal oxide are reached.
(5) The deposition of the metal oxide layer is performed in the deposition chamber 1.
(6) And stopping deposition after the metal oxide layer is deposited to the target thickness.
(7) The pressure in the deposition chamber 1 is controlled by the control part 16 to be balanced with the pressure in the second transition cavity 8, a fourth gate valve between the deposition chamber 1 and the second transition cavity 8 is opened, the substrate is transferred from the deposition chamber 1 to the second transition cavity 8 through the transfer part, and the fourth gate valve is closed.
(8) The second transition chamber 8 begins to release the vacuum until the air pressure in the second transition chamber 8 reaches one atmosphere, the fifth gate valve on the outside of the second transition chamber 8 opens, and the substrate is transferred from the second transition chamber 8 to the second transfer device 14 via the transfer member and then to the subsequent process step.
The following describes a deposition step of a metal oxide layer using IGZO as an example of a material of the metal oxide layer:
Referring to fig. 5, the igzo film growth process may be decomposed into N main cycles, each including N in the main cycle 1 In number of 2 O 3 Sub-cycle, n 2 Ga (P) atoms 2 O 3 Sub-cycle, n 3 And a plurality of ZnO sub-cycles, each sub-cycle comprising the following steps performed in sequence: the method comprises the steps of introducing precursor gas containing single metal element into a deposition chamber, purging the deposition chamber with inert gas, introducing oxidizing gas into the deposition chamber, and purging the deposition chamber with inert gas. Fig. 6 is an exemplary graph of pulse timing for a main cycle and each sub-cycle of an IGZO film growth process. Next, an In is used 2 O 3 Subcycling the steps of the subcycling are illustrated by way of example:
the inert gas output module outputs inert gas to the DADI precursor storage, so that the DADI precursor in a liquid state at normal temperature is converted into DADI gas through the bubbling and heating device, and the inert gas carries the DADI gas into a gas pipeline connected with the DADI precursor output module;
the control module controls a pulse valve on a gas pipeline connected with the DADI precursor output module to be opened in a pulse mode, so that inert gas carries DADI gas into the deposition chamber, and DADI molecules are adsorbed on the surface of the substrate;
the control module controls a pulse valve on a gas pipeline connected with the DADI precursor output module to be closed so as to cut off the transmission of DADI gas to the deposition chamber; and controlling a pulse valve on a gas pipeline connected with the inert gas output module to be opened in a pulse mode, so that inert gas output by the inert gas output module enters the deposition chamber to be purged, and removing redundant DADI molecules which are not adsorbed on the surface of the substrate in the deposition chamber.
The control module controls the pulse valve on the gas pipeline connected with the inert gas output module to be closed and controls the pulse valve on the gas pipeline connected with the ozone output module to be opened In a pulse mode, so that ozone In the ozone output module enters the deposition chamber and reacts with DADI molecules adsorbed on the surface of the substrate to generate In 2 O 3 A film.
The control module is connected with the ozone output module, and a pulse valve on a gas pipeline is closed so as to cut off the transmission of ozone to the deposition chamber; and controlling a pulse valve on a gas pipeline connected with the inert gas output module to be opened in a pulse mode, so that inert gas output by the inert gas output module enters the deposition chamber to be purged, and ozone molecules remained in the deposition chamber are removed.
Ga 2 O 3 Sub-cycle, step of ZnO sub-cycle, and In 2 O 3 The steps of the sub-cycle differ in that the control module controls the pulse valves to be opened differently.
In the description of the present specification, reference to the terms "some embodiments," "other embodiments," "desired embodiments," and the like, means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic descriptions of the above terms do not necessarily refer to the same embodiment or example.
The technical features of the above embodiments may be arbitrarily combined, and for brevity, all of the possible combinations of the technical features of the above embodiments are not described, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples only represent a few embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the claims. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. Accordingly, the scope of protection of the present application is to be determined by the claims appended hereto.

Claims (16)

1. An atomic layer deposition method for depositing a metal oxide layer containing a plurality of metal elements, comprising:
determining the metal element in the metal oxide layer to be deposited as a target element;
obtaining a target proportion group of the corresponding component proportion of each target element;
acquiring a first reference proportion group and first-order process parameters corresponding to the first reference proportion group according to the target proportion group, wherein the first reference proportion group is a first-order historical proportion group closest to the target proportion group in a plurality of first-order historical proportion group data of different component proportions corresponding to each target element;
Determining a second-order technological parameter according to the proportion difference value corresponding to each target element in the target proportion group and the first reference proportion group;
the metal oxide layer is deposited in response to the first order process parameter and the second order process parameter.
2. The atomic layer deposition method according to claim 1, wherein the step of depositing a metal oxide layer comprises: performing a deposition process in a plurality of main cycles; wherein any one of the main cycles comprises: performing deposition according to the generation sequence of the oxide corresponding to each target element and the target number of sub-cycles for each target element in sequence;
wherein the first-order process parameters comprise the cycle times of the sub-cycles corresponding to each target element;
the second-order process parameters comprise pulse width of precursor gas corresponding to each target element.
3. The atomic layer deposition method according to claim 2, wherein, in the process parameters corresponding to the different first-order history proportion groups, pulse widths of the precursor gas corresponding to the same target element are the same, and cycle times of the sub-cycles corresponding to the same target element are different.
4. The atomic layer deposition method according to claim 2, wherein the step of determining the second-order process parameter according to the ratio difference value corresponding to each target element in the target ratio set and the first reference ratio set includes: and determining the regulation direction and regulation range of each target element corresponding to the second-order technological parameter according to the proportion difference value corresponding to each target element in the target proportion group and the first reference proportion group.
5. The atomic layer deposition method according to claim 4, further comprising:
after determining the regulation direction and regulation range of each target element corresponding to the second-order process parameter, acquiring a second reference proportion group and the second-order process parameter corresponding to the second reference proportion group according to the target proportion group; the second reference proportion group is a second-order history proportion group which is the same as the target proportion group in a plurality of second-order history proportion group data of different component proportions corresponding to each target element.
6. The atomic layer deposition method according to claim 5, wherein, in the process parameters corresponding to the second-order history proportion groups, the number of cycles of the sub-cycles corresponding to the same target element is the same, and pulse widths of the precursor gas corresponding to the same target element are different.
7. The atomic layer deposition method according to claim 6, wherein at least one of pulse widths of respective target elements corresponding to precursor supplies is incremented by a preset time interval, the preset time interval being 10ms to 20ms.
8. The atomic layer deposition method according to any one of claims 1 to 6, wherein the kinds of the target elements are three; the step of obtaining a first reference proportion group according to the target proportion group comprises the following steps:
sequentially linking coordinate axes of the corresponding component proportions of each target element into a first triangular coordinate system;
marking the first-order historical proportion group data of the corresponding component proportion of each target element in the first triangular coordinate system according to a first identification;
marking the target proportion group of the corresponding component proportion of each target element in the first triangular coordinate system according to a second identifier;
and determining a first mark closest to the second mark in the first triangular coordinate system, and taking a first-order history proportion group corresponding to the first mark as the first reference proportion group.
9. The atomic layer deposition method according to any one of claims 5 to 7, wherein the kinds of the target elements are three; the step of obtaining a second reference proportion group according to the target proportion group comprises the following steps:
Sequentially linking coordinate axes of the target elements corresponding to the component proportions into a second triangular coordinate system;
marking the second-order historical proportion group data of the corresponding component proportion of each target element in the second triangular coordinate system according to a second identifier;
marking the target proportion group of the corresponding component proportion of each target element in the second triangular coordinate system according to a second identifier;
and determining a second mark closest to the second mark in the second triangular coordinate system, and taking a second-order history proportion group corresponding to the second mark as the second reference proportion group.
10. The atomic layer deposition method according to any one of claims 1 to 6, wherein the metal oxide layer is a metal oxide semiconductor layer.
11. The atomic layer deposition method according to claim 10, wherein the material of the metal oxide semiconductor layer comprises indium gallium zinc oxide.
12. The atomic layer deposition method according to claim 11, wherein the precursor gas for depositing the indium gallium zinc oxide comprises an indium source gas, a gallium source gas, and a zinc source gas; the pulse width of the indium source gas is 0.1s-2s, the pulse width of the gallium source gas is 20ms-200ms, and the pulse width of the zinc source gas is 20ms-200ms.
13. The atomic layer deposition method according to any one of claims 1 to 6, further comprising:
acquiring a growth rate curve of the oxide corresponding to each target element at different temperatures;
and determining a target growth temperature of the oxide corresponding to each target element according to each growth rate curve, wherein the slope of the growth rate curve of the oxide corresponding to each target element is smaller at the target growth temperature.
14. The atomic layer deposition method according to claim 13, wherein the target growth temperature of the oxide corresponding to each of the target elements is the same.
15. An atomic layer deposition system, comprising:
a deposition chamber for depositing a metal oxide layer on a substrate, the metal oxide layer comprising a plurality of metal elements;
the parameter determining module is used for determining the metal element in the metal oxide layer to be deposited as a target element, obtaining a target proportion group corresponding to the component proportion of each target element, obtaining a first reference proportion group and first-order process parameters corresponding to the first reference proportion group according to the target proportion group, and determining second-order process parameters according to the proportion difference value corresponding to each target element in the target proportion group and the first reference proportion group;
The storage module is connected with the parameter determination module and is used for storing first-order historical proportion group data and process parameters of the corresponding component proportions of each target element;
the gas supply device is connected with the deposition chamber and is used for supplying reaction gas to the deposition chamber, and the reaction gas at least comprises precursors corresponding to each target element;
the control module is connected with the parameter determination module and the air supply device and is configured to: the gas supply device is controlled to supply a reactive gas to the deposition chamber in response to the first order process parameter and the second order process parameter.
16. The atomic layer deposition system according to claim 15, further comprising:
one or more serially connected preheating chambers located at a substrate transfer front side of the deposition chamber for preheating the temperature of the substrate.
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