Chemical source co-doped atomic layer deposition method
By adopting the method of chemical source co-doping in the atomic layer deposition process, and by combining multiple supercycles and subcycles, the problems of long coating time and large inert gas use in the prior art are solved, and a more efficient process flow and lower cost are achieved.
Patent Information
- Application Number
- CN202510374103.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-27
- Publication Date
- 2025-06-06
AI Technical Summary
In the existing atomic layer deposition composite film process, the method of cycling deposition of a film by a single ALD leads to a long coating time and a large amount of inert gas, which cannot meet the mass production needs and increases operating costs.
Atomic layer deposition method is adopted for co-doping of chemical sources. Through multiple supercycles, each supercycle includes multiple subcycles. Two or more chemical sources are passed at the same time in the subcycle, and the total number of ALD cycles is reduced by adjusting the order and combination of chemical sources.
It shortens the coating time, reduces the amount of inert gas, improves process efficiency, reduces costs, and meets mass production needs.
Smart Images
Figure CN120099496A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of atomic layer deposition, and more specifically, to a chemical source co-doping atomic layer deposition method. Background Art
[0002] With the development of coating technology, atomic layer deposition (ALD) composite film process has been widely used in various semiconductor technologies. Atomic layer deposition is a method of forming a deposited film by alternately passing gaseous precursors into a reactor and chemically reacting on the surface of the substrate. This technology can deposit materials on the substrate surface layer by layer in the form of a single atomic layer film.
[0003] In the existing atomic layer deposition composite film process, a single ALD cycle is generally used to deposit a film to prepare a composite film of a predetermined ratio and type. Figure 1 As shown, A, B, C are chemical sources (precursor gases), X is a co-reactant, a, b, c are the number of times chemical sources A, B, C are introduced (dose), and N is the total number of cycles of composite film ABC·X. Take method 1 as an example: first, chemical source A and co-reactant X are introduced to deposit A·X monolayer film (A·X sub-cycle), and a total of a cycles are made, then chemical source B and co-reactant X are introduced to deposit B·X monolayer film (B·X sub-cycle), and a total of b cycles are made, and finally chemical source C and co-reactant X are introduced to deposit C·X monolayer film (C·X sub-cycle), and the sequence of A·X monolayer film, B·X monolayer film, and C·X monolayer film (super cycle) is followed N times to complete the preparation of ABC·X composite film, where a, b, c and N are integers, and the bracket represents an ALD sub-cycle. The preparation logic of other methods 2 to 6 is consistent with that of method 1, and only the order of introduction of chemical sources A, B, and C is changed.
[0004] However, this approach has the following problems: Disadvantage 1: In the prior art, a single ALD cycle is generally used to deposit a film to prepare a composite film of a predetermined ratio and type. This method requires an inert gas purge step after each chemical source is introduced, which increases the single cycle time and greatly increases the total coating time, thereby reducing the production capacity of the ALD machine and failing to meet mass production needs.
[0005] Disadvantage 2: The inert gas purge step after each chemical source is introduced increases the amount of inert gas used, thereby increasing the machine operation cost and the total film preparation cost. Summary of the invention
[0006] In view of this, an object of the present invention is to provide a chemical source co-doping atomic layer deposition method to solve the problems existing in the prior art.
[0007] To achieve the above object, the technical solution of the present invention is as follows: A chemical source co-doped atomic layer deposition method is used to deposit a composite film on a substrate, wherein the composite film includes at least two components, each component is obtained by reacting a corresponding chemical source and a reaction gas, and the reaction gas corresponding to each component is the same and is a co-reactant; The method comprises: Perform multiple super cycles, each super cycle includes sequentially performing m sub cycles, where m is a positive integer; each sub cycle includes sequentially introducing a chemical source, introducing a purge gas, introducing a co-reactant, and introducing a purge gas when it is cycled once; Wherein, in at least one sub-cycle, two or more chemical sources are introduced simultaneously; After each sub-cycle is completed, the next sub-cycle is executed until all sub-cycles are completed, completing a super-cycle. The super cycle is repeatedly performed until a composite film of a preset thickness is obtained.
[0008] Furthermore, the method further comprises: Determine the total number of cycles of each chemical source in a supercycle, and simultaneously determine the number of cycles of each subcycle; the total number of cycles of a chemical source in a supercycle is equal to the sum of the number of cycles of the subcycles into which the corresponding chemical source is introduced in a supercycle; Execute the current sub-cycle, and determine whether the number of cycles of each chemical source reaches the number of cycles of the corresponding chemical source in one super cycle after the number of cycles of the current sub-cycle is completed; If the total number of cycles of one of the chemical sources has not been reached, the chemical source continues to be introduced in the remaining sub-cycles until the total number of cycles is reached.
[0009] Further, after the number of cycles of a sub-cycle is completed, the total number of cycles of at least one chemical source is reached.
[0010] Furthermore, at least two chemical sources are introduced simultaneously in the first sub-cycle; And the number of cycles of the first sub-cycle is equal to the number of cycles corresponding to the smallest total number of cycles among the chemical sources introduced.
[0011] Furthermore, all chemical sources are introduced simultaneously in the first sub-cycle.
[0012] Furthermore, the number of cycles of the first sub-cycle is set to the number with the smallest total number of cycles in the chemical source; In the nth sub-cycle, at least one of the remaining chemical sources is introduced, and the number of cycles of the nth sub-cycle is set to the number of cycles with the least number of remaining cycles in the current chemical sources introduced, where n is an integer greater than or equal to 2.
[0013] Furthermore, in the nth sub-cycle, all remaining chemical sources are introduced at the same time, and the number of cycles of the nth sub-cycle is set to the number with the least remaining number of the total number of cycles of the currently introduced chemical sources.
[0014] Furthermore, the composite membrane includes three components corresponding to three chemical sources.
[0015] Furthermore, the total number of cycles corresponding to the three chemical sources in one supercycle are not equal.
[0016] Compared with the prior art, the present invention has the following advantages: The deposition method provided by the present invention adopts the method of simultaneously introducing different chemical sources to carry out the ALD process; only the combination method and the introduction order of each chemical source are changed, thereby reducing the total number of ALD cycles, shortening the coating time, and reducing the amount of purge gas such as inert gas, thereby improving the process efficiency and reducing the process cost. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 Schematic diagram of a conventional deposition process in the prior art; wherein A, B, and C are different chemical sources; X is a co-reactant; a, b, and c are the number of times the chemical sources A, B, and C are dosed, respectively; and N is the total number of cycles of the composite film ABC·X; Figure 2 Schematic diagram of the experimental scheme designed for the present invention. DETAILED DESCRIPTION
[0018] Embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. Although certain embodiments of the present invention are shown in the accompanying drawings, it should be understood that the present invention can be implemented in various forms and should not be construed as being limited to the embodiments described herein, which are instead provided for a more thorough and complete understanding of the present invention. It should be understood that the drawings and embodiments of the present invention are only for exemplary purposes and are not intended to limit the scope of protection of the present invention.
[0019] It should be understood that the various steps described in the method embodiments of the present invention may be performed in different orders and / or in parallel. In addition, the method embodiments may include additional steps and / or omit the steps shown. The scope of the present invention is not limited in this respect.
[0020] The term "including" and its variations used in this document are open inclusions, that is, "including but not limited to". The term "based on" means "based at least in part on". The term "one embodiment" means "at least one embodiment"; the term "another embodiment" means "at least one other embodiment"; the term "some embodiments" means "at least some embodiments". Relevant definitions of other terms will be given in the following description. It should be noted that the concepts of "first", "second", etc. mentioned in the present invention are only used to distinguish different devices, modules or units, and are not used to limit the order or interdependence of the functions performed by these devices, modules or units.
[0021] It should be noted that the modifications of "one", "multiple", "once" and "multiple times" mentioned in the present invention are illustrative rather than restrictive, and those skilled in the art should understand that, unless otherwise clearly indicated in the context, they should be understood as "one or more".
[0022] Unless otherwise specified, the materials and reagents used in the present invention can be obtained from commercial products in the art.
[0023] Based on the above description, an embodiment of the present invention provides a chemical source co-doped atomic layer deposition method, which is used to deposit a composite film on a substrate (such as a wafer), wherein the composite film includes at least two components, each component is obtained by reacting a corresponding chemical source and a reaction gas, and the reaction gas corresponding to each component is the same and is a co-reactant; Optionally, the chemical source can be an inorganic precursor, a metal organic precursor, etc., such as titanium tetrachloride (TiCl 4 ), silicon tetrachloride (SiCl 4 )、trimethylaluminum (TMA), cyclopentadienyl iron (Fe(C 5 H 5 ) 2 ), dicyclopentadienyl nickel (Ni(C 5 H 5 ) 2 )、Diethylzinc(Zn(NH 2 C 2 H 5 ) 2 ), trimethylindium (TMI), tetramethyltin (TDMASn), etc. The co-reactant may be water vapor or oxygen for depositing oxides, or ammonia for depositing nitrides. In the embodiment of the present invention, different chemical sources are represented by A, B, C, etc., and the co-reactant is represented by X.
[0024] The method provided in the embodiment of the present invention includes: Perform multiple super cycles, each super cycle includes m sub cycles executed in sequence, m is a positive integer; each sub cycle includes the following processes in sequence when it is cycled once: introducing a chemical source to be adsorbed on a substrate, introducing a purge gas to remove excess chemical sources, introducing a co-reactant to react with the chemical source in the chamber to obtain a corresponding compound, and introducing a purge gas to remove excess co-reactant; the purge gas may be an inert gas or nitrogen; Among them, two or more chemical sources are introduced in at least one sub-cycle; it can be understood that when only one chemical source is introduced in each sub-cycle, each sub-cycle corresponds to a single-layer film of the introduced chemical source, which is a traditional ALD process in the background technology, such as Figure 1 In this embodiment, at least two or more chemical sources are introduced into at least one sub-cycle, such as Figure 2 As shown, a composite membrane corresponding to more than two chemical sources can be obtained in this sub-cycle; of course, Figure 2 The scheme shown in is only a part of the combination of this embodiment; After each sub-cycle is completed, the next sub-cycle is executed until all sub-cycles are completed, completing a super-cycle. The super cycle is repeatedly performed until a composite film of a preset thickness is obtained.
[0025] In some embodiments, when the proportions of various components in the composite membrane to be prepared are the same, that is, the total number of cycles corresponding to each chemical source in a super cycle is the same, m can be 1. At this time, there can be only one sub-cycle in a super cycle, and the super cycle is the sub-cycle. In this sub-cycle, the precursors corresponding to all components are introduced at the same time. After all the precursors are introduced, the purge gas is introduced, and then the co-reactants are introduced to react, thereby shortening the total cycle time, improving the process efficiency, and also reducing the amount of purge gas used.
[0026] If the proportions between the components are different, the total number of times each chemical source corresponds to a super cycle will be different. If the proportion is small, the total number of cycles will be small, and if the proportion is large, the corresponding total number of cycles will be large. At this time, m is an integer greater than 1. For example, if there are three chemical sources and the proportion of each is different, there will be three sub-cycles in a super cycle.
[0027] It should be noted that, in the embodiment of the present invention, a sub-cycle and a sub-cycle have different meanings. For example, in a super cycle, there are 3 different sub-cycles. In a super cycle, the number of cycles of each sub-cycle can be set separately, such as the number of cycles of the first sub-cycle corresponds to 3 times, the number of cycles of the second sub-cycle corresponds to 5 times, and the number of cycles of the third sub-cycle corresponds to 7 times. That is, in this example, a super cycle has 3 sub-cycles, and the sum of the number of cycles of the 3 sub-cycles is 15 times.
[0028] That is, a super cycle includes multiple sub cycles, and the number of cycles of each sub cycle can be the same or different, which is specifically determined according to the proportion of each component in the composite membrane; in some embodiments, if it is not necessary to precisely define the proportion of each component in the composite membrane, and only a composite membrane composed of multiple components needs to be prepared, there is no need to determine the total number of cycles of each chemical source in a super cycle.
[0029] Of course, when performing a wafer coating process, a composite film of a specific ratio is generally required to be coated. Therefore, in order to accurately obtain a composite film of a specific ratio, in some embodiments, the method includes determining in advance the total number of cycles of each chemical source in a super cycle, and determining the number of cycles of each sub-cycle; the total number of cycles of a chemical source in a super cycle is equal to the sum of the number of cycles of the sub-cycles in which the corresponding chemical source is introduced in a super cycle; Then, the current sub-cycle is executed, and after the number of cycles of the current sub-cycle is completed, it is determined whether the number of cycles of each chemical source reaches the number of cycles of the corresponding chemical source in one super-cycle; If the total number of cycles of one of the chemical sources has not been reached, the chemical source will continue to be introduced in the remaining sub-cycles until the total number of cycles in one super cycle is reached.
[0030] Optionally, the total number of cycles of each chemical source in a super cycle can be determined according to the ratio of the composite film to be prepared. Generally, it can be calibrated in advance, that is, deposition is performed according to different process parameters (number of sub-cycles, deposition time, flow rate, etc.), and then the ratio of the final film is measured to determine the final required process, which can determine the total number of cycles of each chemical source in a super cycle corresponding to a certain composite ratio.
[0031] Preferably, after the number of cycles in a sub-cycle is completed, the total number of cycles of at least one chemical source is reached, thereby avoiding the need to continue to introduce the chemical source in subsequent sub-cycles. The total number of cycles of a chemical source can be completed directly after the number of cycles in a sub-cycle is completed.
[0032] In some embodiments, at least two chemical sources are introduced simultaneously in the first sub-cycle; And the number of cycles of the first sub-cycle is equal to the minimum number of cycles corresponding to the total number of cycles (in one super cycle) of the chemical sources introduced. For example, chemical sources A and B are introduced at the same time in the first sub-cycle, where the total number of cycles corresponding to chemical source A in one super cycle is a times, and the total number of cycles corresponding to chemical source B in one super cycle is b times, and a is greater than b, then the number of cycles of the first sub-cycle can be directly set to b times. If it is greater than b, the content of the component corresponding to chemical source B in the final composite film does not meet the standard; if it is less than b, chemical source B needs to be introduced again in subsequent sub-cycles, affecting the deposition efficiency.
[0033] In some embodiments, all chemical sources can be introduced simultaneously in the first sub-cycle. In this case, if all chemical sources include A, B and C, the total number of cycles of chemical source A in one super cycle is a times, the total number of cycles of chemical source B in one super cycle is b times, and the total number of cycles of chemical source C in one super cycle is c times; wherein b is the smallest; in the first sub-cycle, chemical sources A, chemical source B and chemical source C are introduced simultaneously, and the number of cycles of the first sub-cycle can be set to b times, that is, after the number of cycles of the first sub-cycle is completed, the total number of cycles of chemical source B can be reached; it can be understood that each sub-cycle corresponds to the introduction of co-reactant X, that is, the deposition of compound BX can be completed; of course, part of compound AX and compound CX will also be deposited, but since the content of both in the composite is greater than compound BX, it is necessary to continue to deposit in subsequent sub-cycles to meet the corresponding proportion of the final composite film; After the first sub-cycle is completed, the second sub-cycle is carried out. In the second sub-cycle, only chemical source A or chemical source C can be introduced. When only chemical source A is introduced, the number of cycles of the second sub-cycle is ab times, reaching the total number of cycles of chemical source A. In the third sub-cycle, only chemical source C is introduced. The number of cycles of the third sub-cycle is cb times, reaching the total number of cycles of chemical source C.
[0034] Alternatively, chemical source A and chemical source C can be introduced into the second sub-cycle at the same time. If a is greater than c, the number of cycles of the second sub-cycle is set to cb times, reaching the total number of cycles of chemical source C. At this time, only chemical source A needs to be introduced into the third sub-cycle, and the number of cycles of the third sub-cycle is ac times, reaching the total number of cycles of chemical source A; finally, a super cycle is completed; at this time, in the overall super cycle, the sum of the number of cycles of each sub-cycle is the smallest, the total deposition time is shortened the most, and the amount of purge gas used is the smallest.
[0035] After completing one super cycle, a composite film of a certain thickness and a specific proportion can be obtained, and then the super cycle is repeated until a composite film of a preset thickness is obtained and the process can be stopped.
[0036] Below Figure 2 Taking scheme 1 in the example, the entire ALD process sequence can be designed as follows: First, compound AB X is deposited: in the first step, chemical source A and chemical source B are introduced at the same time (dose A+B); in the second step, an inert gas is introduced for purging (purge); in the third step, a co-reactant X is introduced (dose X); in the fourth step, an inert gas is introduced for purging (purge); these four steps are repeated b times. Then continue to deposit compound AX: in the first step, chemical source A is introduced (dose A); in the second step, an inert gas is introduced for purging (purge); in the third step, a co-reactant X is introduced (dose X); in the fourth step, an inert gas is introduced for purging (purge); these four steps are repeated (ab) times. Finally, compound CX is deposited: in the first step, chemical source C is introduced (dose C); in the second step, an inert gas is introduced for purging (purge); in the third step, a co-reactant X is introduced (dose X); in the fourth step, an inert gas is introduced for purging (purge); these four steps are repeated c times. The deposition order and number of compounds ABX, AX and CX are cycled N times to finally obtain a composite film ABCX of a predetermined ratio. Wherein a, b, c and N are integers, and the bracket represents an ALD sub-cycle.
[0037] Among them, a super cycle includes: compound AB X sub-cycle, compound AX sub-cycle and compound CX sub-cycle, a total of three sub-cycles; the number of cycles of the compound AB X sub-cycle is b times, the number of cycles of the compound AX sub-cycle is (ab) times, and the number of cycles of the compound CX sub-cycle is c times. The number of cycles of the super cycle is N times.
[0038] Similarly, the preparation logic of other methods 2 to 9 is consistent with that of method 1, and only the combination and introduction order of chemical sources A, B, and C are changed. The combination and introduction order of chemical sources A, B, and C are not limited to the above 9 schemes, and are combined according to actual film layer requirements, mainly considering shortening the total deposition time and reducing gas consumption.
[0039] In summary, the new design of the present invention adopts the method of introducing different chemical sources simultaneously to carry out the ALD process. Only the combination and order of the introduction of each chemical source are changed, which reduces the total number of ALD cycles, shortens the coating time, and reduces the amount of inert gas used, thereby improving process efficiency and reducing costs.
[0040] If Figure 1According to Scheme 1 in (Prior Art), the total number of ALD cycles is (a+b+c)×N. Assuming that the cycle time (cycle time, one time) of the ALD sub-cycles are t1, t2, and t3, that is, the time for depositing compound AX sub-cycle is t1, the time for depositing compound BX sub-cycle is t2, and the time for depositing compound CX sub-cycle is t3, the total cycle time is (a×t1+b×t2+c×t3)×N.
[0041] right Figure 2 According to Scheme 8 in (New Scheme), the total number of ALD cycles is (a+cb)×N. Assume that the cycle time (cycle time, one time) of the ALD sub-cycles is t1, t2, and t3, respectively. Among them, the first sub-cycle is the deposition of compound ABC X sub-cycle, and its cycle time is t2 (i.e., the corresponding deposition of compound BX sub-cycle, the time is t2). The remaining chemical sources A and C continue in the subsequent sub-cycles. In this scheme, the second sub-cycle is to continue to deposit chemical source C, that is, to deposit compound CX sub-cycle, and its time corresponds to t3; the third sub-cycle is to continue to deposit chemical source A, that is, to deposit compound AX sub-cycle, and its time corresponds to t1; then the total cycle time is [(ab)×t1+b×t2+(cb)×t3]×N.
[0042] Compared with the existing solutions, the technical solution of the present invention reduces the total cycle time by b×(t1+t3)×N. Other combinations of the technical solution of the present invention can also shorten the total cycle time, improve the process efficiency to varying degrees, and reduce the cost compared with the existing solutions.
[0043] The above is only an example. The combination of chemical sources A, B, and C and the order of introduction are not limited to Figure 2 The chemical source may also include only chemical sources A and B, or include chemical sources A, B, C, D, and so on.
[0044] The following is a description of the specific implementation process: Preparation of sample 1: SiAlO: Bis(diethylamino)silane·(BDEAS) and trimethylaluminum(TMA) were used as precursors, respectively. 3 As the co-reactant, Ar as the purge gas, the reaction temperature is 200℃, and the SiAlO composite film is prepared (the sub-cycles of SiO and AlO are 3 times and 1 time respectively, and the super-cycle is 50 times). The specific steps are as follows: First, compound SiAlO was deposited: in the first step, chemical source BDEAS and chemical source TMA were introduced at the same time, with carrier gas flow rates of 200 sccm and 100 sccm respectively, for 2 s; in the second step, Ar (500 sccm) was introduced for 5 s of purge; in the third step, the co-reactant O was introduced 3 , time is 5s; fourth step, introduce Ar (500sccm) for 3s; these four steps are performed once. Then the compound SiO is deposited: first step, introduce chemical source BDEAS, carrier gas flow rate is 200sccm, time is 2s; second step, introduce Ar (500sccm) for 5s; third step, introduce co-reactant O 3 , time is 5s; in the fourth step, Ar (500sccm) is introduced for purging for 3s; these four steps are performed for 2 sub-cycles in total. All sub-cycles are performed for 50 super-cycles in this order and number to complete the preparation of SiAlO composite film, and the film thickness and X-ray photoelectron spectroscopy (XPS) test are performed on the film.
[0045] The total time for preparing sample 1 was 37.5 min; the amount of Ar used was 11167 mL.
[0046] Preparation of sample 2: HfAlZrN trimethylaluminum (TMA), tetrakis(diethylamino)hafnium (HfEt 2 ) 4 )、Tetrakis(dimethylamino)zirconium(Zr(NMe 2 ) 4 ) is the precursor, NH 3 As the co-reactant, Ar as the purge gas, the reaction temperature is 350℃, and the HfAlZrN composite film is prepared (the sub-cycles of AlN, HfN, and ZrN are (1 time, 3 times, and 1 time, respectively, and the super-cycle is 40 times). The specific steps are as follows: First, the compound HfAlN is deposited: In the first step, the chemical source TMA and the chemical source Hf(NEt 2 ) 4 , the carrier gas flow rates were 100 sccm and 200 sccm, respectively, for 2 s; the second step was to introduce Ar (800 sccm) for 5 s of purge; the third step was to introduce the co-reactant NH 3 , flow rate is 500sccm, time is 5s; fourth step, Ar (800sccm) is introduced for 3s; these four steps are performed once. Then the compound HfZrN is deposited: in the first step, the chemical source Hf (NEt 2 ) 4 and chemical source Zr(NMe 2 ) 4, the carrier gas flow rates were 200 sccm and 100 sccm, respectively, for 2 s; the second step was to introduce Ar (800 sccm) for 5 s of purge; the third step was to introduce the co-reactant NH 3 , flow rate is 500sccm, time is 5s; fourth step, introduce Ar (800sccm) for 3s; these four steps are performed once; finally, compound HfN is deposited: first step, introduce chemical source Hf(NEt 2 ) 4 , the carrier gas flow rate is 200 sccm, and the time is 2s; the second step is to introduce Ar (800 sccm) for 5s; the third step is to introduce the co-reactant NH 3 , the flow rate is 500sccm, and the time is 5s; the fourth step is to introduce Ar (800sccm) for purging for 3s; these four steps are performed for a total of 1 sub-cycle. All sub-cycles are performed in this order and number of times for 40 super cycles to complete the preparation of HfAlZrN composite film, and the film thickness and X-ray photoelectron spectroscopy (XPS) test are performed on the film.
[0047] The total preparation time of sample 2 was 30 min; the amount of Ar used was 13866 mL; NH 3 Dosage: 5000mL.
[0048] Preparation sample 3: SiAlO (according to traditional process) Bis(diethylamino)silane·(BDEAS) and trimethylaluminum(TMA) were used as precursors, respectively. 3 As the co-reactant, Ar as the purge gas, the reaction temperature is 200℃, and the SiAlO composite film is prepared (the sub-cycles of SiO and AlO are 3 times and 1 time respectively, and the super-cycle is 50 times). The specific steps are as follows: First, the compound AlO was deposited: in the first step, the chemical source TMA was introduced, the carrier gas flow rate was 100 sccm, and the time was 2s; in the second step, Ar (500 sccm) was introduced for 5s; in the third step, the co-reactant O was introduced 3 , time is 5s; fourth step, introduce Ar (500sccm) for purging for 3s; these four steps are performed once for a total of one sub-cycle. Then, compound SiO is deposited. In the first step, chemical source BDEAS is introduced with a carrier gas flow rate of 200sccm for 2s; second step, Ar (500sccm) is introduced for purging for 5s; third step, co-reactant O is introduced 3 , time is 5s; fourth step, Ar (500sccm) is introduced for purging for 3s; these four steps are performed for 3 sub-cycles in total. All sub-cycles are performed for 50 super-cycles in this order and number to complete the preparation of SiAlO composite film, and the film thickness and X-ray photoelectron spectroscopy (XPS) test are performed on the film.
[0049] The total time for preparing sample 3 was 50 min; the amount of Ar used was 14500 mL.
[0050] Preparation sample 4: HfAlZrN (according to traditional process) Trimethylaluminum (TMA), tetrakis(diethylamino)hafnium (H(NEtz)4), tetrakis(dimethylamino)zirconium (Zr(NMe 2 ) 4 ) is the precursor, NH 3 As the co-reactant, Ar as the purge gas, reaction temperature 350℃, prepare HfAlZrN composite film (AlN, HfN, ZrN sub-cycles are 1, 3, 1 respectively, and super cycle is 40 times), the specific steps are as follows: First, the compound HfN is deposited: In the first step, the chemical source Hf(NEt 2 ) 4 , the carrier gas flow rate is 200 sccm, and the time is 2s; the second step is to introduce Ar (800 sccm) for 5s; the third step is to introduce the co-reactant NH 3 , flow rate is 500sccm, time is 5s; fourth step, Ar (800sccm) is introduced for purging for 3s; these four steps are carried out for 3 sub-cycles. Then the compound AlN is deposited: first step, chemical source TMA is introduced, carrier gas flow rate is 100sccm, time is 2s; second step, Ar (800sccm) is introduced for purging for 5s; third step, co-reactant NH 3 , flow rate is 500sccm, time is 5s; fourth step, introduce Ar (800sccm) for 3s; these four steps are performed once; finally, compound ZrN is deposited: first step, introduce chemical source Zr(NMe 2 ) 4 , the carrier gas flow rate is 100 sccm, and the time is 2s; the second step is to introduce Ar (800 sccm) for 5s; the third step is to introduce the co-reactant NH 3 , the flow rate is 500sccm, and the time is 5s; the fourth step is to introduce Ar (800sccm) for purging for 3s; these four steps are performed for a total of 1 sub-cycle. All sub-cycles are performed in this order and number of times for 40 super cycles to complete the preparation of HfAlZN composite film, and the film thickness and X-ray photoelectron spectroscopy (XPS) test are performed on the film.
[0051] The total preparation time of sample 4 was 50 min; the amount of Ar used was 22400 mL; NH 3 Dosage: 8333mL.
[0052] The prepared samples were tested for film thickness and XPS, and the results are shown in Tables 1 and 2 below: Table 1:
[0053] Table 2:
[0054] Through calculation, the preparation time of sample 1 is shortened by 25% and the Ar usage is reduced by 23% compared with sample 3; the preparation time of sample 2 is shortened by 40% and the Ar usage is reduced by 38% compared with sample 4. It can be seen that the method provided by the present invention can significantly shorten the process time and reduce the use of inert gas while successfully preparing a composite film in proportion.
[0055] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0056] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.
Claims
1. A chemical source co-doping atomic layer deposition method, characterized in that: Used to deposit a composite film on a substrate, wherein the composite film includes at least two components, each component is obtained by reacting a corresponding chemical source and a reaction gas, and the reaction gas corresponding to each component is the same and serves as a co-reactant; The method comprises: Perform multiple super cycles, each super cycle includes sequentially performing m sub cycles, where m is a positive integer; each sub cycle includes sequentially introducing a chemical source, introducing a purge gas, introducing a co-reactant, and introducing a purge gas when it is cycled once; Wherein, in at least one sub-cycle, two or more chemical sources are introduced simultaneously; After each sub-cycle is completed, the next sub-cycle is executed until all sub-cycles are completed, completing a super-cycle. The super cycle is repeatedly performed until a composite film of a preset thickness is obtained.
2. The method according to claim 1, characterized in that The method further comprises: Determine the total number of cycles of each chemical source in a supercycle, and simultaneously determine the number of cycles of each subcycle; the total number of cycles of a chemical source in a supercycle is equal to the sum of the number of cycles of the subcycles into which the corresponding chemical source is introduced in a supercycle; Execute the current sub-cycle, and determine whether the number of cycles of each chemical source reaches the number of cycles of the corresponding chemical source in one super cycle after the number of cycles of the current sub-cycle is completed; If the total number of cycles of one of the chemical sources has not been reached, the chemical source continues to be introduced in the remaining sub-cycles until the total number of cycles is reached.
3. The method according to claim 2, characterized in that After the number of cycles in a sub-cycle is completed, the total number of cycles for at least one chemical source is reached.
4. The method according to claim 2, characterized in that: In the first sub-cycle, at least two chemical sources are introduced simultaneously; And the number of cycles of the first sub-cycle is equal to the number of cycles corresponding to the smallest total number of cycles among the chemical sources introduced.
5. The method according to claim 2, characterized in that: In the first sub-cycle, all chemical sources are introduced simultaneously.
6. The method according to claim 5, characterized in that The number of cycles in the first subcycle is set to the number that minimizes the total number of cycles in the chemical source; In the nth sub-cycle, at least one of the remaining chemical sources is introduced, and the number of cycles of the nth sub-cycle is set to the number of cycles with the least number of remaining cycles in the current chemical sources introduced, where n is an integer greater than or equal to 2.
7. The method according to claim 6, characterized in that In the nth sub-cycle, all the remaining chemical sources are introduced at the same time, and the number of cycles of the nth sub-cycle is set to the number with the least remaining number of the total number of cycles of the currently introduced chemical sources.
8. The method according to any one of claims 1 to 7, characterized in that: The composite membrane includes three components corresponding to three chemical sources.
9. The method according to claim 8, characterized in that The total number of cycles corresponding to the three chemical sources in one supercycle is not equal.