CN117476441B - Patterning architecture method for silicon wafer surface - Google Patents

Patterning architecture method for silicon wafer surface Download PDF

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CN117476441B
CN117476441B CN202311816412.8A CN202311816412A CN117476441B CN 117476441 B CN117476441 B CN 117476441B CN 202311816412 A CN202311816412 A CN 202311816412A CN 117476441 B CN117476441 B CN 117476441B
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silicon wafer
deposition
film
parts
cyclohexene
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CN117476441A (en
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陈庆敏
李丙科
陈加朋
卓倩武
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Wuxi Songyu Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02178—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing aluminium, e.g. Al2O3
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
    • H01L21/02304—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment formation of intermediate layers, e.g. buffer layers, layers to improve adhesion, lattice match or diffusion barriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02334—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment in-situ cleaning after layer formation, e.g. removing process residues

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Abstract

The invention relates to the technical field of semiconductors and discloses a graph for the surface of a silicon waferA method of patterning structure. The invention forms a coating by arranging an adhesion material on a non-deposition area of a silicon wafer substrate, and then carries out Al by adjusting the atomic layer deposition temperature to be not lower than 300 DEG C 2 O 3 Thin film deposition such that Al 2 O 3 The film is deposited in the area outside the non-deposition area to realize Al 2 O 3 Selective deposition of thin films to pattern architecture Al on silicon wafer surfaces 2 O 3 A film for promoting the separation of the adhesion material from the silicon wafer in the non-deposition area of the silicon wafer substrate during the deposition process, al 2 O 3 The coating is easy to remove after the film is deposited. The selective deposition method provided by the invention deposits the obtained Al in a specific area 2 O 3 The film has good uniformity. In microelectronic device fabrication, different materials or films are required for different parts to perform specific functions, and the present invention provides a method of area selective deposition that can achieve these functional requirements.

Description

Patterning architecture method for silicon wafer surface
Technical Field
The invention relates to the technical field of semiconductors, in particular to a patterning architecture method for a silicon wafer surface.
Background
The semiconductor industry is faced with many challenges in pursuing device miniaturization involving rapid scaling of nanoscale features. These problems include the introduction of complex manufacturing steps such as multiple lithographic steps and integration of high performance materials. In order to keep pace with the miniaturization of devices, selective deposition has shown an effective prospect, as it is possible to eliminate costly photolithography steps by simplifying the integration scheme.
Selective deposition of materials can be achieved in a variety of ways. The chemical precursors can selectively react with one surface over the other (e.g., metal and dielectric). Process parameters such as pressure, substrate temperature, precursor partial pressure, and/or gas flow may be adjusted to adjust the chemical kinetics of a particular surface reaction. Another possible approach involves surface pretreatment that can be used to activate or deactivate surfaces of interest to the introduced film deposition precursor.
To realize the complex patterning architecture of next generation semiconductor devices, the conventional top-down (top-down) approach consisting of multiple photolithography and etching steps results in high costs and faces the challenge of technology node scaling. There is a continuing need in the art for methods for improving deposition selectivity.
Bottom-up area selective atomic layer deposition (AS-ALD) has been increasingly used to implement patterned architectures with nano-control. However, the defects of the regioselective atomic layer deposition are: when the deposited ALD film becomes thicker than the self-assembled monolayer used to passivate non-growing surfaces, the ALD film may grow laterally, i.e., creating a mushroom growth (mushrooming) problem, thereby reducing selectivity.
To solve the "mushroom growth" problem during selective deposition, there is a problem in the prior art that by directly forming a thicker protective self-assembled monolayer, the method has the following problems: the precursor is delivered in the vapor phase and an excessively thick self-assembled monolayer can prevent the attachment of the precursor to the desired deposited area, thereby causing non-uniformity in the selectively deposited film.
Therefore, in view of the foregoing, there is a need in the art for a new method for improving deposition selectivity, which avoids the problem of "mushroom growth" during the deposition of regioselective atomic layers, which makes the deposited film non-uniform, and further avoids the degradation of semiconductor performance.
Disclosure of Invention
In order to solve the technical problem of the complex patterning structure of the semiconductor, the invention provides a patterning structure method for the surface of a silicon wafer. The invention forms a coating by coating an adhesion material on a non-deposition area of a silicon wafer substrate, and then carries out Al by adjusting the atomic layer deposition temperature to be not lower than 300 DEG C 2 O 3 Thin film deposition such that Al 2 O 3 The film is deposited in the area outside the non-deposition area to realize Al 2 O 3 Selective deposition of the film, separation of the adhesion material on the non-deposition area of the silicon wafer substrate from the silicon wafer in the deposition process, and cleaning of the silicon wafer to obtain surface Al 2 O 3 Thin film patterned structured silicon wafer.
The specific technical scheme of the invention is as follows:
the invention provides a patterning architecture method for a silicon wafer surface, which comprises the following steps:
step S1: providing an attachment material;
step S2: coating the adhesion material on a non-deposition area of a silicon wafer substrate;
step S3: regulating the temperature of an atomic layer deposition cavity to be not lower than 300 ℃, putting the silicon wafer substrate processed in the step S2 into the atomic layer deposition cavity, and carrying out Al by using an atomic layer deposition technology 2 O 3 Depositing a film, and promoting the separation of the attached material on the non-deposition area of the silicon wafer substrate from the silicon wafer in the deposition process;
step S4: cleaning the silicon wafer to remove the adhesion material and Al deposited on the surface of the adhesion material 2 O 3 Thin film, thereby obtaining Al on the surface of the silicon wafer 2 O 3 Film pattern.
The adhesive material is coated on the non-deposition area of the silicon substrate, and is coated on Al 2 O 3 Can prevent Al during film deposition 2 O 3 Depositing a film in a non-deposition area of the silicon wafer; when the atomic layer deposition film is carried out, the temperature in the atomic deposition cavity is higher, and the Al is finished 2 O 3 After the film deposition, the adhesion material is subjected to high-temperature treatment, so that the adhesion material is separated from the silicon wafer, is easy to fall off from the surface of the silicon wafer and is easy to remove. The invention forms a coating by coating an adhesion material on a non-deposition area of a silicon wafer substrate, and then carries out Al by adjusting the atomic layer deposition temperature to be not lower than 300 DEG C 2 O 3 Thin film deposition such that Al 2 O 3 The film is deposited in the area outside the non-deposition area to realize Al 2 O 3 Selective deposition of the film, separation of the adhesion material on the non-deposition area of the silicon wafer substrate from the silicon wafer in the deposition process, and cleaning of the silicon wafer to obtain surface Al 2 O 3 Thin film patterned structured silicon wafer.
In the above technical solution of the present invention, in step S1, the adhesive material is a resin, and the viscosity of the resin becomes smaller after the resin is placed in a high-temperature environment.
Further preferably, the resin is a cyclohexene-modified polyimide resin.
The coating layer is arranged on the non-deposition area of the silicon substrate, which can prevent Al deposition in the atomic layer 2 O 3 Precursor gases adhere to non-deposition areas of the silicon wafer substrate during the thin film process. The researchers of the invention find that when cyclohexene modified polyimide resin is used as a coating layer and the atomic layer deposition temperature is not lower than 300 ℃, the cyclohexene structure therein can be cracked and opened, and the deposition of Al is completed 2 O 3 In the cooling process of the silicon wafer after the film, structural rearrangement and cyclization of cyclohexene structure are carried out, so that the interface layer structure of the resin is changed and is easy to fall off from the surface of the silicon wafer.
In order to solve the problem of the regional selective atomic layer deposition, the invention provides a cyclohexene modified polyimide resin which is coated on a non-deposition region of a silicon wafer substrate to form a coating, and then Al is carried out by adjusting the atomic layer deposition temperature to be not lower than 300 DEG C 2 O 3 Thin film deposition such that Al 2 O 3 The film is deposited in the area outside the non-deposition area to realize Al 2 O 3 Selective deposition of thin film to realize Al on silicon wafer surface 2 O 3 Patterning structure of the film.
The invention realizes Al 2 O 3 The selective deposition of the film has the advantage that the cyclohexene modified polyimide resin can prevent Al as a coating layer in the deposition process 2 O 3 Depositing the film in a non-deposition area; after the silicon wafer is cooled, the cyclohexene structure in the cyclohexene modified polyimide resin is cracked in a high-temperature environment, and in the cooling process of cooling, structural rearrangement and cyclization of the cyclohexene structure again occur, so that the interface layer structure of the resin coating is changed and is easy to fall off from the surface of the silicon wafer, and therefore, the coating of a non-deposition area is easy to remove.
As a preferable mode of the above technical scheme of the invention, the raw materials of the cyclohexene modified polyimide resin comprise the following components in parts by weight:
100 parts of 4,4'- (hexafluoroisopropenyl) isophthalic anhydride, 80-110 parts of 4,4' -diaminodiphenylmethane, 20-40 parts of maleic anhydride and 20-50 parts of 5-methylfurfuryl amine.
The invention prepares polyimide resin by taking 4,4'- (hexafluoro-isopropenyl) diphthalic anhydride and 4,4' -diaminodiphenyl methane as monomers, introduces substituted olefin into polyimide through maleic anhydride, introduces conjugated diene through 5-methylfurylamine, introduces cyclohexene structure into polyimide resin through Diels-Alder reaction, and can crack and open loop when the cyclohexene structure is not lower than 300 ℃ so as to finish Al deposition 2 O 3 In the cooling process of the silicon wafer after the film, the cyclohexene structure is re-cyclized, and in the re-cyclizing process, structural rearrangement occurs, so that the interface layer structure of the resin is changed, and the resin is easy to fall off from the surface of the silicon wafer.
Further preferably, the raw materials of the cyclohexene-modified polyimide resin further comprise the following components in parts by weight:
5-10 parts of triethylamine and 5-15 parts of acetic anhydride.
Triethylamine is used as a catalyst for preparing cyclohexene modified polyimide resin, and acetic anhydride is used as a dehydrating agent.
As the preferable mode of the technical scheme, in the step S3, the temperature of the atomic layer deposition cavity is regulated to 300-400 ℃.
The temperature of the deposition process affects the cleavage of the cyclohexene structure and the rearrangement process in the resin structure. The temperature of the atomic layer deposition cavity is preferably regulated to 300-400 ℃, and the temperature can lead the cyclohexene structure to be cracked, and is favorable for replacing olefin and conjugated diene to be rearranged in the resin structure, so that the interface layer structure of the resin is changed. If the temperature during deposition is less than 300 ℃, cyclohexene structure is difficult to crack, the subsequent structural rearrangement process cannot be carried out, and resin is difficult to fall off from the surface of the silicon wafer; if the temperature is higher than 400 ℃ during deposition, the substituted olefin and the conjugated diene are difficult to recycle after cooling, the adhesive force between the resin and the silicon wafer is still strong, the resin is difficult to fall off from the surface of the silicon wafer, and meanwhile, the Al obtained by deposition 2 O 3 The film quality is poor.
As a preferable mode of the above-mentioned technical scheme of the present invention, in step S3, al 2 O 3 The thickness of the film is 1-10 nm.
As a preferable mode of the above technical scheme of the invention, al 2 O 3 The method for depositing the film comprises the following steps: circulating and introducing precursor gas trimethylaluminum and precursor gas H into the atomic layer deposition cavity 2 O, and nitrogen is introduced after each precursor gas is introduced.
The cycle times and the gas inlet time influence the residence time of the cyclohexene modified polyimide resin coating in the environment of 300-400 ℃ so as to influence the cracking of the cyclohexene structure and the rearrangement process in the resin structure. If the residence time of the cyclohexene modified polyimide resin coating is too short, the cyclohexene structure is not completely cracked, the rearrangement of substituted olefin and conjugated diene in the resin structure can be influenced, the adhesive force between the resin and the silicon wafer after cooling is still strong, and the resin is not easy to fall off from the surface of the silicon wafer. If the residence time is too long, the resin coating is at high temperature for a long time, the substituted olefin and the conjugated diene are difficult to recycle after being cooled, the adhesive force between the resin and the silicon wafer is still strong, and the resin is difficult to fall off from the surface of the silicon wafer.
Preferably, the number of cycles is 10 to 40.
Preferably, the time of introducing trimethylaluminum is 3-7 s in each cycle.
Preferably, H in each cycle 2 The time of O is 3-7 s.
Preferably, the flow rate of nitrogen gas is 10-30L/min and the time of nitrogen gas is 5-10 s.
Compared with the prior art, the invention has the following technical effects:
the adhesive material is coated on the non-deposition area of the silicon substrate, and is coated on Al 2 O 3 Can prevent Al during film deposition 2 O 3 Depositing a film in a non-deposition area of the silicon wafer; when the atomic layer deposition film is carried out, the temperature in the atomic deposition cavity is higher, and the Al is finished 2 O 3 After the film deposition, the adhesion material is subjected to high-temperature treatment, so that the adhesion material is separated from the silicon wafer, is easy to fall off from the surface of the silicon wafer and is easy to remove. The invention forms a coating by coating an adhesion material on a non-deposition area of a silicon wafer substrate, and then adjusts the atomic layer deposition temperature to be not lower thanAl at 300 DEG C 2 O 3 Thin film deposition such that Al 2 O 3 The film is deposited in the area outside the non-deposition area to realize Al 2 O 3 Selective deposition of the film, separation of the adhesion material on the non-deposition area of the silicon wafer substrate from the silicon wafer in the deposition process, and cleaning of the silicon wafer to obtain surface Al 2 O 3 Thin film patterned structured silicon wafer. In microelectronic device fabrication, different materials or films are required for different parts to perform specific functions, such as the front side deposition of films but not the back side deposition of silicon wafers, the method of the present invention can achieve these functional requirements, such as Al 2 O 3 And (3) single-sided deposition of the film.
The invention forms a coating by coating cyclohexene modified polyimide resin on a non-deposition area of a silicon wafer substrate, and then carries out Al by adjusting the atomic layer deposition temperature to be not lower than 300 DEG C 2 O 3 Thin film deposition such that Al 2 O 3 The film is deposited in the area outside the non-deposition area to realize Al 2 O 3 Selective deposition of thin films.
The invention forms a coating on the non-deposition area of the silicon substrate by cyclohexene modified polyimide resin, and the cyclohexene modified polyimide resin can be used as a coating to prevent Al in the deposition process 2 O 3 Depositing the film in a non-deposition area; after the silicon wafer is cooled, the cyclohexene structure in the cyclohexene modified polyimide resin is cracked in a high-temperature environment, and in the cooling process of cooling, structural rearrangement and cyclization of the cyclohexene structure again occur, so that the interface layer structure of the resin coating is changed and is easy to fall off from the surface of the silicon wafer, and therefore, the coating of a non-deposition area is easy to remove.
The selective deposition method provided by the invention deposits the obtained Al in a specific area 2 O 3 The film has good uniformity.
Drawings
FIG. 1 is a schematic illustration of a selective deposition on a silicon wafer substrate in accordance with the present invention;
FIG. 2 is a graph showing the film thickness and uniformity test results;
FIG. 3 shows the results of residual amounts of resins in examples 1 to 9
FIG. 4 shows the results of the residual amounts of the resins of comparative examples 1 to 10.
Marked in the figure as: 1. deposition area, 2, non-deposition area.
Detailed Description
The invention is further described below with reference to examples. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
Example 1
A patterning architecture method for a silicon wafer surface comprises the following steps S1-S3:
step S1: preparation of cyclohexene-modified polyimide resin:
(1) The following raw materials are taken according to parts by weight: 100 parts of 4,4'- (hexafluoroisopropenyl) isophthalic anhydride, 90 parts of 4,4' -diaminodiphenylmethane, 30 parts of maleic anhydride, 40 parts of 5-methylfurfuryl amine, 8 parts of triethylamine, 10 parts of acetic anhydride and 1000 parts of N, N-dimethylformamide.
(2) 4,4'- (hexafluoroisopropenyl) diphthalic anhydride and 4,4' -diaminodiphenyl methane were mixed in N, N-dimethylformamide and subjected to preliminary reaction at 25℃for 5 hours to obtain a polyamic acid solution.
(3) Then adding maleic anhydride, 5-methyl furfuryl amine, acetic anhydride and triethylamine into the polyamic acid solution, and reacting again at 25 ℃ for 8 hours to obtain cyclohexene modified polyimide resin. Wherein the polymerization degree of polyimide is 100.
Step S2: as shown in FIG. 1, the silicon wafer substrate is divided into a deposition region 1 and a non-deposition region 2, where Al is to be deposited 2 O 3 Thin film, non-deposition area does not deposit Al 2 O 3 A film. Coating the cyclohexene modified polyimide resin provided in the step S1 on a silicon waferAnd forming a film with the thickness of 4nm in a non-deposition area of the substrate.
Step S3: regulating the temperature of the atomic layer deposition cavity to 350 ℃, putting the silicon wafer substrate processed in the step S2 into the atomic layer deposition cavity, and then circularly introducing precursor gas trimethylaluminum and precursor gas H into the atomic layer deposition cavity 2 O, and after each time of leading in the precursor gas, leading in nitrogen to realize Al 2 O 3 And (5) depositing a film. Al (Al) 2 O 3 And after the film deposition is completed, the boat is moved back and cooled.
Wherein the number of cycles is 30. In each cycle, the trimethyl aluminum is introduced for 5s, H 2 The O-in time was 5s. And each time nitrogen is introduced, the flow rate of the introduced nitrogen is 20L/min, and the time is 7s.
Step S4: and (3) cleaning the silicon wafer by using ionized water to obtain the silicon wafer with the surface pattern.
Example 2
A patterning architecture method for a silicon wafer surface comprises the following steps S1-S3:
step S1: preparation of cyclohexene-modified polyimide resin:
(1) The following raw materials are taken according to parts by weight: 100 parts of 4,4'- (hexafluoroisopropenyl) isophthalic anhydride, 90 parts of 4,4' -diaminodiphenylmethane, 30 parts of maleic anhydride, 40 parts of 5-methylfurfuryl amine, 8 parts of triethylamine, 10 parts of acetic anhydride and 1000 parts of N, N-dimethylformamide.
(2) 4,4'- (hexafluoroisopropenyl) diphthalic anhydride and 4,4' -diaminodiphenyl methane were mixed in N, N-dimethylformamide and subjected to preliminary reaction at 25℃for 5 hours to obtain a polyamic acid solution.
(3) Then adding maleic anhydride, 5-methyl furfuryl amine, acetic anhydride and triethylamine into the polyamic acid solution, and reacting again at 25 ℃ for 8 hours to obtain cyclohexene modified polyimide resin. Wherein the polymerization degree of polyimide is 100.
Step S2: as shown in FIG. 1, the silicon wafer substrate is divided into a deposition region 1 and a non-deposition region 2, where Al is to be deposited 2 O 3 Thin film, non-deposition area does not deposit Al 2 O 3 A film. And (3) coating the cyclohexene modified polyimide resin provided in the step (S1) on a non-deposition area of a silicon wafer substrate to form a film with the thickness of 4 nm.
Step S3: regulating the temperature of the atomic layer deposition cavity to 300 ℃, putting the silicon wafer substrate processed in the step S2 into the atomic layer deposition cavity, and then circularly introducing precursor gas trimethylaluminum and precursor gas H into the atomic layer deposition cavity 2 O, and after each time of leading in the precursor gas, leading in nitrogen to realize Al 2 O 3 And (5) depositing a film. Al (Al) 2 O 3 And after the film deposition is completed, the boat is moved back and cooled.
Wherein the number of cycles is 30. In each cycle, the trimethyl aluminum is introduced for 5s, H 2 The O-in time was 5s. And each time nitrogen is introduced, the flow rate of the introduced nitrogen is 20L/min, and the time is 7s.
Step S4: and (3) cleaning the silicon wafer by using ionized water to obtain the silicon wafer with the surface pattern.
Example 3
A patterning architecture method for a silicon wafer surface comprises the following steps S1-S3:
step S1: preparation of cyclohexene-modified polyimide resin:
(1) The following raw materials are taken according to parts by weight: 100 parts of 4,4'- (hexafluoroisopropenyl) isophthalic anhydride, 90 parts of 4,4' -diaminodiphenylmethane, 30 parts of maleic anhydride, 40 parts of 5-methylfurfuryl amine, 8 parts of triethylamine, 10 parts of acetic anhydride and 1000 parts of N, N-dimethylformamide.
(2) 4,4'- (hexafluoroisopropenyl) diphthalic anhydride and 4,4' -diaminodiphenyl methane were mixed in N, N-dimethylformamide and subjected to preliminary reaction at 25℃for 5 hours to obtain a polyamic acid solution.
(3) Then adding maleic anhydride, 5-methyl furfuryl amine, acetic anhydride and triethylamine into the polyamic acid solution, and reacting again at 25 ℃ for 8 hours to obtain cyclohexene modified polyimide resin. Wherein the polymerization degree of polyimide is 100.
Step S2: as shown in FIG. 1, the silicon wafer substrate is divided into a deposition region 1 and a non-deposition region 2, the deposition regionTo be deposited with Al 2 O 3 Thin film, non-deposition area does not deposit Al 2 O 3 A film. And (3) coating the cyclohexene modified polyimide resin provided in the step (S1) on a non-deposition area of a silicon wafer substrate to form a film with the thickness of 4 nm.
Step S3: regulating the temperature of the atomic layer deposition cavity to 400 ℃, putting the silicon wafer substrate processed in the step S2 into the atomic layer deposition cavity, and then circularly introducing precursor gas trimethylaluminum and precursor gas H into the atomic layer deposition cavity 2 O, and after each time of leading in the precursor gas, leading in nitrogen to realize Al 2 O 3 And (5) depositing a film. Al (Al) 2 O 3 And after the film deposition is completed, the boat is moved back and cooled.
Wherein the number of cycles is 30. In each cycle, the trimethyl aluminum is introduced for 5s, H 2 The O-in time was 5s. And each time nitrogen is introduced, the flow rate of the introduced nitrogen is 20L/min, and the time is 7s.
Step S4: and (3) cleaning the silicon wafer by using ionized water to obtain the silicon wafer with the surface pattern.
Example 4
A patterning architecture method for a silicon wafer surface comprises the following steps S1-S3:
step S1: preparation of cyclohexene-modified polyimide resin:
(1) The following raw materials are taken according to parts by weight: 100 parts of 4,4'- (hexafluoroisopropenyl) isophthalic anhydride, 90 parts of 4,4' -diaminodiphenylmethane, 20 parts of maleic anhydride, 40 parts of 5-methylfurfuryl amine, 8 parts of triethylamine, 10 parts of acetic anhydride and 1000 parts of N, N-dimethylformamide.
(2) 4,4'- (hexafluoroisopropenyl) diphthalic anhydride and 4,4' -diaminodiphenyl methane were mixed in N, N-dimethylformamide and subjected to preliminary reaction at 25℃for 5 hours to obtain a polyamic acid solution.
(3) Then adding maleic anhydride, 5-methyl furfuryl amine, acetic anhydride and triethylamine into the polyamic acid solution, and reacting again at 25 ℃ for 8 hours to obtain cyclohexene modified polyimide resin. Wherein the polymerization degree of polyimide is 100.
Step S2: as shown in the figure1, dividing a silicon wafer substrate into a deposition area 1 and a non-deposition area 2, wherein the deposition area is to deposit Al 2 O 3 Thin film, non-deposition area does not deposit Al 2 O 3 A film. And (3) coating the cyclohexene modified polyimide resin provided in the step (S1) on a non-deposition area of a silicon wafer substrate to form a film with the thickness of 4 nm.
Step S3: regulating the temperature of the atomic layer deposition cavity to 350 ℃, putting the silicon wafer substrate processed in the step S2 into the atomic layer deposition cavity, and then circularly introducing precursor gas trimethylaluminum and precursor gas H into the atomic layer deposition cavity 2 O, and after each time of leading in the precursor gas, leading in nitrogen to realize Al 2 O 3 And (5) depositing a film. Al (Al) 2 O 3 And after the film deposition is completed, the boat is moved back and cooled.
Wherein the number of cycles is 30. In each cycle, the trimethyl aluminum is introduced for 5s, H 2 The O-in time was 5s. And each time nitrogen is introduced, the flow rate of the introduced nitrogen is 20L/min, and the time is 7s.
Step S4: and (3) cleaning the silicon wafer by using ionized water to obtain the silicon wafer with the surface pattern.
Example 5
A patterning architecture method for a silicon wafer surface comprises the following steps S1-S3:
step S1: preparation of cyclohexene-modified polyimide resin:
(1) The following raw materials are taken according to parts by weight: 100 parts of 4,4'- (hexafluoroisopropenyl) isophthalic anhydride, 90 parts of 4,4' -diaminodiphenylmethane, 40 parts of maleic anhydride, 40 parts of 5-methylfurfuryl amine, 8 parts of triethylamine, 10 parts of acetic anhydride and 1000 parts of N, N-dimethylformamide.
(2) 4,4'- (hexafluoroisopropenyl) diphthalic anhydride and 4,4' -diaminodiphenyl methane were mixed in N, N-dimethylformamide and subjected to preliminary reaction at 25℃for 5 hours to obtain a polyamic acid solution.
(3) Then adding maleic anhydride, 5-methyl furfuryl amine, acetic anhydride and triethylamine into the polyamic acid solution, and reacting again at 25 ℃ for 8 hours to obtain cyclohexene modified polyimide resin. Wherein the polymerization degree of polyimide is 100.
Step S2: as shown in FIG. 1, the silicon wafer substrate is divided into a deposition region 1 and a non-deposition region 2, where Al is to be deposited 2 O 3 Thin film, non-deposition area does not deposit Al 2 O 3 A film. And (3) coating the cyclohexene modified polyimide resin provided in the step (S1) on a non-deposition area of a silicon wafer substrate to form a film with the thickness of 4 nm.
Step S3: regulating the temperature of the atomic layer deposition cavity to 350 ℃, putting the silicon wafer substrate processed in the step S2 into the atomic layer deposition cavity, and then circularly introducing precursor gas trimethylaluminum and precursor gas H into the atomic layer deposition cavity 2 O, and after each time of leading in the precursor gas, leading in nitrogen to realize Al 2 O 3 And (5) depositing a film. Al (Al) 2 O 3 And after the film deposition is completed, the boat is moved back and cooled.
Wherein the number of cycles is 30. In each cycle, the trimethyl aluminum is introduced for 5s, H 2 The O-in time was 5s. And each time nitrogen is introduced, the flow rate of the introduced nitrogen is 20L/min, and the time is 7s.
Step S4: and (3) cleaning the silicon wafer by using ionized water to obtain the silicon wafer with the surface pattern.
Example 6
A patterning architecture method for a silicon wafer surface comprises the following steps S1-S3:
step S1: preparation of cyclohexene-modified polyimide resin:
(1) The following raw materials are taken according to parts by weight: 100 parts of 4,4'- (hexafluoroisopropenyl) isophthalic anhydride, 90 parts of 4,4' -diaminodiphenylmethane, 30 parts of maleic anhydride, 20 parts of 5-methylfurfuryl amine, 8 parts of triethylamine, 10 parts of acetic anhydride and 1000 parts of N, N-dimethylformamide.
(2) 4,4'- (hexafluoroisopropenyl) diphthalic anhydride and 4,4' -diaminodiphenyl methane were mixed in N, N-dimethylformamide and subjected to preliminary reaction at 25℃for 5 hours to obtain a polyamic acid solution.
(3) Then adding maleic anhydride, 5-methyl furfuryl amine, acetic anhydride and triethylamine into the polyamic acid solution, and reacting again at 25 ℃ for 8 hours to obtain cyclohexene modified polyimide resin. Wherein the polymerization degree of polyimide is 100.
Step S2: as shown in FIG. 1, the silicon wafer substrate is divided into a deposition region 1 and a non-deposition region 2, where Al is to be deposited 2 O 3 Thin film, non-deposition area does not deposit Al 2 O 3 A film. And (3) coating the cyclohexene modified polyimide resin provided in the step (S1) on a non-deposition area of a silicon wafer substrate to form a film with the thickness of 4 nm.
Step S3: regulating the temperature of the atomic layer deposition cavity to 350 ℃, putting the silicon wafer substrate processed in the step S2 into the atomic layer deposition cavity, and then circularly introducing precursor gas trimethylaluminum and precursor gas H into the atomic layer deposition cavity 2 O, and after each time of leading in the precursor gas, leading in nitrogen to realize Al 2 O 3 And (5) depositing a film. Al (Al) 2 O 3 And after the film deposition is completed, the boat is moved back and cooled.
Wherein the number of cycles is 30. In each cycle, the trimethyl aluminum is introduced for 5s, H 2 The O-in time was 5s. And each time nitrogen is introduced, the flow rate of the introduced nitrogen is 20L/min, and the time is 7s.
Step S4: and (3) cleaning the silicon wafer by using ionized water to obtain the silicon wafer with the surface pattern.
Example 7
A patterning architecture method for a silicon wafer surface comprises the following steps S1-S3:
step S1: preparation of cyclohexene-modified polyimide resin:
(1) The following raw materials are taken according to parts by weight: 100 parts of 4,4'- (hexafluoroisopropenyl) isophthalic anhydride, 90 parts of 4,4' -diaminodiphenylmethane, 30 parts of maleic anhydride, 50 parts of 5-methylfurfuryl amine, 8 parts of triethylamine, 10 parts of acetic anhydride and 1000 parts of N, N-dimethylformamide.
(2) 4,4'- (hexafluoroisopropenyl) diphthalic anhydride and 4,4' -diaminodiphenyl methane were mixed in N, N-dimethylformamide and subjected to preliminary reaction at 25℃for 5 hours to obtain a polyamic acid solution.
(3) Then adding maleic anhydride, 5-methyl furfuryl amine, acetic anhydride and triethylamine into the polyamic acid solution, and reacting again at 25 ℃ for 8 hours to obtain cyclohexene modified polyimide resin. Wherein the polymerization degree of polyimide is 100.
Step S2: as shown in FIG. 1, the silicon wafer substrate is divided into a deposition region 1 and a non-deposition region 2, where Al is to be deposited 2 O 3 Thin film, non-deposition area does not deposit Al 2 O 3 A film. And (3) coating the cyclohexene modified polyimide resin provided in the step (S1) on a non-deposition area of a silicon wafer substrate to form a film with the thickness of 4 nm.
Step S3: regulating the temperature of the atomic layer deposition cavity to 350 ℃, putting the silicon wafer substrate processed in the step S2 into the atomic layer deposition cavity, and then circularly introducing precursor gas trimethylaluminum and precursor gas H into the atomic layer deposition cavity 2 O, and after each time of leading in the precursor gas, leading in nitrogen to realize Al 2 O 3 And (5) depositing a film. Al (Al) 2 O 3 And after the film deposition is completed, the boat is moved back and cooled.
Wherein the number of cycles is 30. In each cycle, the trimethyl aluminum is introduced for 5s, H 2 The O-in time was 5s. And each time nitrogen is introduced, the flow rate of the introduced nitrogen is 20L/min, and the time is 7s.
Step S4: and (3) cleaning the silicon wafer by using ionized water to obtain the silicon wafer with the surface pattern.
Example 8
A patterning architecture method for a silicon wafer surface comprises the following steps S1-S3:
step S1: preparation of cyclohexene-modified polyimide resin:
(1) The following raw materials are taken according to parts by weight: 100 parts of 4,4'- (hexafluoroisopropenyl) isophthalic anhydride, 80 parts of 4,4' -diaminodiphenylmethane, 30 parts of maleic anhydride, 40 parts of 5-methylfurfuryl amine, 5 parts of triethylamine, 15 parts of acetic anhydride and 800 parts of N, N-dimethylformamide.
(2) 4,4'- (hexafluoroisopropenyl) diphthalic anhydride and 4,4' -diaminodiphenyl methane were mixed in N, N-dimethylformamide and subjected to preliminary reaction at 25℃for 5 hours to obtain a polyamic acid solution.
(3) Then adding maleic anhydride, 5-methyl furfuryl amine, acetic anhydride and triethylamine into the polyamic acid solution, and reacting again at 25 ℃ for 8 hours to obtain cyclohexene modified polyimide resin. Wherein the polymerization degree of polyimide is 100.
Step S2: as shown in FIG. 1, the silicon wafer substrate is divided into a deposition region 1 and a non-deposition region 2, where Al is to be deposited 2 O 3 Thin film, non-deposition area does not deposit Al 2 O 3 A film. And (3) coating the cyclohexene modified polyimide resin provided in the step (S1) on a non-deposition area of a silicon wafer substrate to form a film with the thickness of 4 nm.
Step S3: regulating the temperature of the atomic layer deposition cavity to 350 ℃, putting the silicon wafer substrate processed in the step S2 into the atomic layer deposition cavity, and then circularly introducing precursor gas trimethylaluminum and precursor gas H into the atomic layer deposition cavity 2 O, and after each time of leading in the precursor gas, leading in nitrogen to realize Al 2 O 3 And (5) depositing a film. Al (Al) 2 O 3 And after the film deposition is completed, the boat is moved back and cooled.
Wherein the number of cycles is 10. In each cycle, the trimethyl aluminum is introduced for 7s, H 2 The O-in time was 7s. And nitrogen is introduced each time, the flow rate of the introduced nitrogen is 10L/min, and the time is 10s.
Step S4: and (3) cleaning the silicon wafer by using ionized water to obtain the silicon wafer with the surface pattern.
Example 9
A patterning architecture method for a silicon wafer surface comprises the following steps S1-S3:
step S1: preparation of cyclohexene-modified polyimide resin:
(1) The following raw materials are taken according to parts by weight: 100 parts of 4,4'- (hexafluoroisopropenyl) isophthalic anhydride, 110 parts of 4,4' -diaminodiphenylmethane, 30 parts of maleic anhydride, 40 parts of 5-methylfurfuryl amine, 10 parts of triethylamine, 5 parts of acetic anhydride and 1200 parts of N, N-dimethylformamide.
(2) 4,4'- (hexafluoroisopropenyl) diphthalic anhydride and 4,4' -diaminodiphenyl methane were mixed in N, N-dimethylformamide and subjected to preliminary reaction at 25℃for 5 hours to obtain a polyamic acid solution.
(3) Then adding maleic anhydride, 5-methyl furfuryl amine, acetic anhydride and triethylamine into the polyamic acid solution, and reacting again at 25 ℃ for 8 hours to obtain cyclohexene modified polyimide resin. Wherein the polymerization degree of polyimide is 100.
Step S2: as shown in FIG. 1, the silicon wafer substrate is divided into a deposition region 1 and a non-deposition region 2, where Al is to be deposited 2 O 3 Thin film, non-deposition area does not deposit Al 2 O 3 A film. And (3) coating the cyclohexene modified polyimide resin provided in the step (S1) on a non-deposition area of a silicon wafer substrate to form a film with the thickness of 4 nm.
Step S3: regulating the temperature of the atomic layer deposition cavity to be not lower than 300 ℃, putting the silicon wafer substrate treated in the step S2 into the atomic layer deposition cavity, and then circularly introducing precursor gases such as trimethylaluminum and precursor gas H into the atomic layer deposition cavity 2 O, and after each time of leading in the precursor gas, leading in nitrogen to realize Al 2 O 3 And (5) depositing a film. Al (Al) 2 O 3 And after the film deposition is completed, the boat is moved back and cooled.
Wherein the number of cycles is 40. In each cycle, the trimethyl aluminum is introduced for 3s, H 2 The O-in time was 3s. And each time nitrogen is introduced, the flow rate of the introduced nitrogen is 30L/min, and the time is 5s.
Step S4: and (3) cleaning the silicon wafer by using ionized water to obtain the silicon wafer with the surface pattern.
Comparative example 1
The main difference from example 1 is that: in step S3, the temperature of the atomic layer deposition chamber is adjusted to 250 ℃.
Comparative example 2
The main difference from example 1 is that: in step S3, the temperature of the atomic layer deposition chamber is adjusted to 450 ℃.
Comparative example 3
The main difference from example 1 is that: in step S3, the number of cycles is 5.
Comparative example 4
The main difference from example 1 is that: in step S3, the number of cycles is 45.
Comparative example 5
The main difference from example 1 is that: in step S1, the part of maleic anhydride was 10 parts.
Comparative example 6
The main difference from example 1 is that: in step S1, the part of maleic anhydride was 50 parts.
Comparative example 7
The main difference from example 1 is that: in step S1, the part of 5-methylfurfuryl amine is 10 parts.
Comparative example 8
The main difference from example 1 is that: in step S1, the fraction of 5-methylfurfuryl amine was 60.
Comparative example 9
The main difference from example 1 is that: in step S1, a polyimide resin was prepared by replacing the raw material dianhydride monomer 4,4' - (hexafluoroisopropenyl) diphthalic anhydride with 3,3', 4' -biphenyl tetracarboxylic dianhydride.
Comparative example 10
The main difference from example 1 is that: in step S1, no 5-methylfurfuryl amine is added, and instead, furfuryl amine is used to introduce conjugated diene into the polyimide resin.
Evaluation of Performance
(1) Deposition of Al from examples 1 to 9 and comparative examples 1 to 10 2 O 3 And taking a piece of silicon wafer from the middle position of the silicon wafer carrier aluminum boat in the silicon wafer obtained after the film, measuring the film thickness by using a laser ellipsometer, and testing the uniformity of the film thickness. The test positions are specifically shown as point a, point B, point C, point D and point E in fig. 1. The uniformity calculation formula is as follows:
in-sheet uniformity = [ (in-sheet film thickness maximum-minimum)/(2×in-sheet film thickness average) ]×100%
The test results are shown in FIG. 2.
(2) Deposition of Al from examples 1 to 9 and comparative examples 1 to 10 2 O 3 Taking a piece of silicon wafer obtained after the film from the middle position of the silicon wafer carrier aluminum boatDetecting the residual quantity of the resin on the surface of the silicon wafer.
The residual amount results of examples 1 to 9 are shown in FIG. 3.
The residual amount results of comparative examples 1 to 10 are shown in FIG. 4.
Data analysis:
(1) As can be seen from the results in fig. 2:
(1) as shown in the data of examples 1 to 9, the present invention forms a coating layer by coating cyclohexene-modified polyimide resin on a non-deposition region of a silicon wafer substrate, and then performs Al by adjusting the atomic layer deposition temperature to not lower than 300 DEG C 2 O 3 Thin film deposition such that Al 2 O 3 The film is deposited in the area outside the non-deposition area to realize Al 2 O 3 Selective deposition of thin films, al 2 O 3 The uniformity in the film piece is good.
(2) But comparative example 2 was significantly less uniform. The main difference between comparative example 2 and example 1 is Al 2 O 3 The temperature at which the film was deposited was 450 c, thus indicating that too high a temperature at the time of deposition affected the uniformity of film deposition. Further analysis of the cause of its effect on uniformity may be: too high a temperature may directly affect the adhesion of the precursor gas to the wafer surface, thereby affecting uniformity.
(3) The uniformity of comparative example 4 was poor. The main difference between comparative example 4 and example 1 is that the number of deposition cycles is 45, thus indicating that the excessive number of cycles during deposition affects the uniformity of thin film deposition. The reasons for this analysis may be: precursor gas is difficult to attach to the surface of the silicon wafer in the later stage of film deposition, so that uniformity is affected.
(2) In the embodiment, 4'- (hexafluoro-isopropenyl) diphthalic anhydride and 4,4' -diaminodiphenyl methane are taken as monomers to prepare polyimide resin, substituted olefin is introduced into polyimide through maleic anhydride, conjugated diene is introduced into polyimide through 5-methyl furamine, cyclohexene structure is introduced into polyimide resin through Diels-Alder reaction, so that cyclohexene modified polyimide resin is obtained, and the cyclohexene modified polyimide resin is coated on a non-deposition area of a silicon wafer substrate to form a coating. As can be seen from the results in fig. 3 and 4:
(1) examples 1 to 9 have smaller resin residual amount, which indicates that the cyclohexene modified polyimide resin is coated on the non-deposition area of the silicon wafer substrate to form a coating layer, and the coating layer is easy to remove and has small residual amount, and further indicates that the method Al provided by the invention 2 O 3 The selective deposition of the film has the prospect of industrial mass production.
(2) The resin residual amount of comparative examples 1-2 was significantly increased as compared with example 1. The main difference between comparative examples 1-2 and example 1 is the temperature at which the film is deposited, which is 250 c, 450 c, respectively, thus indicating that either too low or too high a temperature at the time of deposition affects the removal of the resin. Further analyzing the reasons, introducing substituted olefin into polyimide resin through maleic anhydride, introducing conjugated diene through 5-methylfurfuryl amine, and performing a base Yu Dier SiAlder reaction to introduce cyclohexene structure into polyimide resin to obtain cyclohexene modified polyimide resin, wherein the cyclohexene structure is required to be subjected to cleavage ring opening under a certain temperature condition, and the interface layer structure of the resin is changed in the process of finishing structural rearrangement, so that the resin is easy to fall off from the surface of a silicon wafer. The temperature condition is preferably 300-400 ℃. If the temperature during deposition is less than 300 ℃, cyclohexene structure is difficult to crack and cannot undergo a structure rearrangement process, resin is difficult to fall off from the surface of the silicon wafer, and the residual quantity is obviously increased as shown in data of comparative example 1; if the temperature during deposition is higher than 400 ℃, the substituted olefin and the conjugated diene are difficult to recycle after cooling, the adhesive force between the resin and the silicon wafer is still strong, and the resin is difficult to fall off from the surface of the silicon wafer, as shown in the data of comparative example 2, the residual quantity is obviously increased, and meanwhile, the deposited Al is obtained 2 O 3 The film quality is poor.
(3) The resin residual amounts of comparative examples 3 to 4 were significantly increased as compared with example 1. The main difference between comparative examples 3 to 4 and example 1 is that the precursor gas was circulated 5 times and 45 times, respectively, when depositing a thin film, thereby indicating that too little or too much circulation may affect the removal of the resin. Further analyzing the reason, the cycle times may influence the residence time of the cyclohexene modified polyimide resin coating in the environment of 300-400 ℃ so as to influence the cracking of the cyclohexene structure and the rearrangement process in the resin structure. If the residence time of the cyclohexene modified polyimide resin coating is too short, the cyclohexene structure is not completely cracked, the rearrangement of substituted olefin and conjugated diene in the resin structure can be influenced, the adhesive force between the resin and the silicon wafer after cooling is still strong, and the resin is not easy to fall off from the surface of the silicon wafer. If the residence time is too long, the resin coating is at high temperature for a long time, the substituted olefin and the conjugated diene are difficult to recycle after being cooled, the adhesive force between the resin and the silicon wafer is still strong, and the resin is difficult to fall off from the surface of the silicon wafer.
(4) The resin residual amounts of comparative examples 5 to 8 were increased to a different extent than in example 1. Examples 4 to 7 and comparative examples 5 to 8 the extent of ease of resin removal was characterized by observing the residual amount of resin detachment by adjusting the amount of the introduced substituted olefin, conjugated diene. As is clear from comparative analyses of comparative examples 5 to 8 with examples 1 and examples 4 to 7, the introduction of a substituted olefin into polyimide by maleic anhydride, the introduction of a conjugated diene by 5-methylfurfuryl amine, and the introduction of a cyclohexene structure into polyimide resin by Diels-Alder reaction are required to be within a certain range, and the amount of maleic anhydride and 5-methylfurfuryl amine is required to be increased to a different extent beyond the range.
(5) The resin residual amount of comparative example 9 was slightly increased as compared with example 1. The main difference between comparative example 9 and example 1 is that the polyimide resin was prepared by substituting 3,3', 4' -biphenyltetracarboxylic dianhydride for the starting dianhydride monomer 4,4' - (hexafluoroisopropenyl) diphthalic anhydride. Thus, it is demonstrated that cyclohexene polyimide resins prepared from the dianhydride monomer 4,4' - (hexafluoroisopropenyl) diphthalic anhydride have better shedding-prone properties after high temperature treatment than resins prepared from 3,3', 4' -biphenyl tetracarboxylic dianhydride.
(6) The resin residual amount of comparative example 10 was significantly increased as compared with example 1. The main difference between comparative example 10 and example 1 is that 5-methylfurfuryl amine was not added and instead, furfuryl amine was used to introduce conjugated diene into the polyimide resin. Therefore, the conjugated diene is introduced into the polyimide resin by using the 5-methylfurfuryl amine to carry out Diels-Alder reaction to introduce a cyclohexene structure, which is favorable for structural rearrangement before or during re-cyclization after high-temperature treatment and is favorable for changing the interface layer structure of the resin to lead the resin to be easy to fall off. The difference between the structures of 5-methylfurfuryl amine and furfuryl amine is that the further analysis of the methyl groups on the furan ring is more advantageous for structural rearrangement before or during the re-cyclization, probably because the change of the methyl conformation may promote structural rearrangement and the change of the methyl idea in the 5-methylfurfuryl amine after passing through the high temperature environment of the atomic deposition chamber. Therefore, the 5-methyl furfuryl amine is used for introducing conjugated diene into polyimide resin, and the polyimide resin has the advantage of facilitating the resin to be separated out finally.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.

Claims (7)

1. A patterning architecture method for the surface of a silicon wafer is characterized in that: the method comprises the following steps:
step S1: providing an attachment material;
step S2: coating the adhesion material on a non-deposition area of a silicon wafer substrate;
step S3: regulating the temperature of an atomic layer deposition cavity to be not lower than 300 ℃, putting the silicon wafer substrate processed in the step S2 into the atomic layer deposition cavity, and carrying out Al by using an atomic layer deposition technology 2 O 3 Depositing a film, and promoting the separation of the attached material on the non-deposition area of the silicon wafer substrate from the silicon wafer in the deposition process;
step S4: cleaning the silicon wafer to remove the adhesion material and Al deposited on the surface of the adhesion material 2 O 3 Thin film, thereby obtaining Al on the surface of the silicon wafer 2 O 3 A thin film pattern;
wherein Al is 2 O 3 The method for depositing the film comprises the following steps: circulating and introducing precursor gas trimethylaluminum and precursor gas H into the atomic layer deposition cavity 2 O, and at each passIntroducing nitrogen after the precursor gas is introduced;
in the step S1, the adhesion material is cyclohexene modified polyimide resin; in the step S3, the temperature of the atomic layer deposition cavity is regulated to 300-400 ℃;
the cyclohexene modified polyimide resin takes 4,4'- (hexafluoro-isopropenyl) diphthalic anhydride and 4,4' -diaminodiphenyl methane as monomers, introduces substituted olefin into polyimide through maleic anhydride, introduces conjugated diene through 5-methylfurfuryl amine, and introduces cyclohexene structure into polyimide resin through Diels-Alder reaction, and the preparation method comprises the following steps:
(1) Mixing 4,4'- (hexafluoroisopropenyl) phthalic anhydride and 4,4' -diaminodiphenyl methane into N, N-dimethylformamide, and performing preliminary reaction at 25 ℃ for 5 hours to obtain polyamic acid solution;
(2) And (3) adding maleic anhydride, 5-methyl furfuryl amine, acetic anhydride and triethylamine into the polyamic acid solution, and reacting again at 25 ℃ for 8 hours to obtain cyclohexene modified polyimide resin.
2. A method of patterning a surface of a silicon wafer as set forth in claim 1, wherein: the cyclohexene modified polyimide resin comprises the following raw materials in parts by weight:
100 parts of 4,4'- (hexafluoroisopropenyl) isophthalic anhydride, 80-110 parts of 4,4' -diaminodiphenylmethane, 20-40 parts of maleic anhydride and 20-50 parts of 5-methylfurfuryl amine.
3. A method of patterning a surface of a silicon wafer as set forth in claim 2 wherein: the cyclohexene modified polyimide resin comprises the following raw materials in parts by weight:
5-10 parts of triethylamine and 5-15 parts of acetic anhydride.
4. A method of patterning a surface of a silicon wafer as set forth in claim 1, wherein: in step S3, al 2 O 3 The thickness of the film is 1-10 nm.
5. A method of patterning a surface of a silicon wafer as set forth in claim 1, wherein: in each cycle, the time of introducing trimethylaluminum is 3-7 s.
6. A method of patterning a surface of a silicon wafer as set forth in claim 1, wherein: in each cycle, H 2 The time of O is 3-7 s.
7. A method of patterning a surface of a silicon wafer as set forth in claim 1, wherein: the flow rate of nitrogen gas is 10-30L/min and the time is 5-10 s.
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CN102560419A (en) * 2011-11-29 2012-07-11 华东师范大学 Method for preparing alumina ultrathin film
CN102898645A (en) * 2011-07-28 2013-01-30 财团法人工业技术研究院 Polyimide copolymer and method for producing patterned metal oxide layer

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WO2015008141A2 (en) * 2013-07-16 2015-01-22 King Abdullah University Of Science And Technology Micro-and/or nano-scale patterned porous membranes, methods of making membranes, and methods of using membranes

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Publication number Priority date Publication date Assignee Title
CN102898645A (en) * 2011-07-28 2013-01-30 财团法人工业技术研究院 Polyimide copolymer and method for producing patterned metal oxide layer
CN102560419A (en) * 2011-11-29 2012-07-11 华东师范大学 Method for preparing alumina ultrathin film

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