CN107978513B - Method for preparing film by wet method - Google Patents
Method for preparing film by wet method Download PDFInfo
- Publication number
- CN107978513B CN107978513B CN201711236440.7A CN201711236440A CN107978513B CN 107978513 B CN107978513 B CN 107978513B CN 201711236440 A CN201711236440 A CN 201711236440A CN 107978513 B CN107978513 B CN 107978513B
- Authority
- CN
- China
- Prior art keywords
- film
- annealing
- preparing
- precursor solution
- thin film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
-
- 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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
-
- 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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02656—Special treatments
- H01L21/02664—Aftertreatments
Abstract
The invention discloses a method for preparing a film by a wet method, which comprises the following steps: dissolving a solute metal compound in an organic solvent to obtain a precursor solution; preparing an initial film according to the precursor solution; carrying out early-stage annealing on the initial film; and performing cyclic steam heat treatment for specified times after the early-stage annealing is completed to obtain a finished film. The method can keep the water oxygen rate constant in the steam oxidation annealing treatment process, thereby improving the quality of the active layer film and the insulating layer film and further improving the performance of the thin film transistor.
Description
Technical Field
The invention relates to the field of annealing treatment, in particular to a method for preparing a film by a wet method.
Background
In recent years, thin film transistors have been widely studied as switching devices for active driving of liquid crystal displays and organic light emitting diodes. The vacuum method for preparing the thin film transistor has already begun to be commercialized, but the manufacturing equipment is expensive, the cost is high, and the like, which cannot meet the requirement of low cost. Therefore, there is a need to develop a method for manufacturing a thin film transistor at low cost by ink jet printing, screen printing, solution spin coating, and the like. However, it is difficult to stably obtain high characteristics of the thin film transistor in the active layer and insulating layer thin films prepared by the above methods, and in view of the above problems, the amount of oxygen defects and the defect level can be controlled and the mobility can be improved by preparing the thin film by a wet process, which is a steam oxidation annealing treatment. In addition, the existing steam oxidation annealing technology generally adopts the mode of directly introducing steam, and the oxidation process is not sufficient, so that the defects of rough film surface and low transmittance are caused.
Disclosure of Invention
The invention aims to provide a method for preparing a film by a wet method, which can solve the problems of inconstant water-oxygen rate and poor quality of an active layer film and an insulating layer film in the process of steam oxidation annealing treatment.
In order to achieve the purpose, the invention provides the following scheme:
a wet-process thin film preparation method, comprising:
dissolving a solute metal compound in an organic solvent to obtain a precursor solution;
preparing an initial film according to the precursor solution;
carrying out early-stage annealing on the initial film;
and performing cyclic steam heat treatment for specified times after the early-stage annealing is completed to obtain a finished film.
Optionally, dissolving the solute metal compound in an organic solvent to obtain a precursor solution specifically includes:
dissolving the solute metal compound in the organic solvent according to the mixing molar ratio of the solute metal compound to the organic solvent to obtain a mixed solution;
and mixing and stirring the mixed solution, and obtaining a precursor solution after the mixed solution is clarified.
Optionally, the preparing an initial thin film according to the precursor solution specifically includes:
taking a common glass slide as a substrate, and sequentially carrying out ultrasonic cleaning on the substrate by using analytically pure acetone, alcohol and deionized water;
drying the cleaned substrate;
and smearing the dried substrate according to the precursor solution to obtain an initial film.
Optionally, the performing of the early-stage annealing on the initial thin film specifically includes:
the annealing temperature is 100-200 ℃, the annealing time is 10min, and the atmosphere is air.
Optionally, after the early-stage annealing is completed, performing cyclic steam heat treatment for a specified number of times, and obtaining a finished film specifically includes:
putting the annealed initial film on a quartz boat in an annealing furnace, wherein the temperature of the annealing furnace is increased to 400 ℃ from normal temperature;
introducing water vapor into the annealing furnace, wherein the introduction time of the water vapor is kept for 10 s;
the annealing furnace is dried for 30s at the constant temperature of 400 ℃, and then water vapor is introduced again for the next circulation;
and performing 10-15 times of circulation process to obtain a finished product film.
According to the specific embodiment provided by the invention, the invention discloses the following technical effects:
the wet method for preparing the film adopts a multi-cycle step-by-step mode of introducing water vapor to prepare the film, so that the oxidation reaction is more sufficient, the annealing time is shortened, the surface roughness of the film of the active layer and the insulating layer is reduced, and the transmissivity, the device performance and the quality of the prepared film are improved; and the water vapor is added step by step in a multi-cycle manner, and the amount of the introduced water vapor can be regulated and controlled through the step number.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a flow chart of a wet method for preparing a thin film according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a multi-cycle rapid steam heat treatment cycle in accordance with an embodiment of the present invention;
FIG. 3 is a graph of Atomic Force Microscope (AFM) test results for ZTO films after general annealing and after multi-cycle rapid water vapor heat treatment when preparing zinc tin oxide transparent conductive films according to embodiments of the present invention;
FIG. 4 is the UV spectrophotometer analysis results of ZTO films after general annealing and after multi-cycle rapid water vapor heat treatment when preparing zinc tin oxide transparent conductive films according to embodiments of the present invention;
FIG. 5 is a graph showing the transfer characteristics of a device after a conventional water vapor annealing and after a multi-cycle rapid water vapor heat treatment in the preparation of a zinc tin oxide transparent conductive film according to an embodiment of the present invention;
FIG. 6 shows AFM test results for WZTO films after general annealing and after multi-cycle rapid water vapor heat treatment when preparing a W-Zn-Sn oxide transparent conductive film according to an embodiment of the present invention;
FIG. 7 shows the results of UV spectrophotometer analysis of WZTO films after general annealing and after multi-cycle rapid water vapor heat treatment in the preparation of a tungsten zinc tin oxide transparent conductive film according to an embodiment of the present invention;
FIG. 8 is a graph showing the transfer characteristics of devices after conventional annealing and after multi-cycle rapid water vapor thermal treatment when a transparent conductive film of tungsten-zinc-tin oxide is prepared according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
FIG. 1 is a flow chart of a wet method for preparing a thin film according to an embodiment of the present invention. Referring to fig. 1, a method for preparing a thin film by a wet process includes:
step 101: dissolving a solute metal compound in an organic solvent to obtain a precursor solution;
step 102: preparing an initial film according to the precursor solution;
step 103: carrying out early-stage annealing on the initial film;
step 104: and performing cyclic steam heat treatment for specified times after the early-stage annealing is completed to obtain a finished film.
The operation steps will now be specifically described by taking the preparation of a zinc tin oxide transparent conductive film on a glass substrate material by a wet process film preparation method as an example.
(1) Tin tetrachloride pentahydrate and zinc acetate dihydrate are weighed according to the molar ratio of 3:7 of tin to zinc, and are sequentially poured into 50mL of glycol methyl ether solvent, and then magnetic stirring is carried out. And after the solution is stirred to be clear, uniformly mixed precursor solution with the molar concentration of 0.3mol/L is obtained, and certain monoethanolamine is added to ensure that the molar ratio of the ion concentration in the solution to the monoethanolamine is 1.
(2) And heating the prepared precursor solution in a water bath for 70 ℃, and keeping the temperature for 3 hours to form a ZTO solution.
(3) And (3) using a common glass slide as a substrate, respectively carrying out ultrasonic cleaning on the substrate by using analytically pure acetone, alcohol and deionized water to clean the glass substrate, and carrying out ink-jet printing on a zinc tin oxide solution after drying to pattern the initial film.
(4) And pre-annealing after the initial film is printed, wherein the annealing temperature is 150 ℃, the annealing time is 10 minutes, and the atmosphere is air.
(5) And (3) putting the initial film into a quartz boat in an annealing furnace, raising the temperature of the annealing furnace from normal temperature to 400 ℃, opening a connection switch with a water vapor generating device, disconnecting the connection for 10s, keeping the constant temperature of 400 ℃, drying for 30s, and then introducing water vapor again for the next circulation. The number of the above-mentioned circulation process is 12 times. FIG. 2 is a schematic diagram of a multi-cycle rapid steam heat treatment cycle according to an embodiment of the present invention, and it can be seen that a cycle of multiple cycles of steam heat treatment is adopted in the present application.
FIG. 3 is a graph of AFM test results for ZTO films after conventional annealing and after the above-described rapid water vapor heat treatment of multiple cycles in the preparation of zinc tin oxide transparent conductive films according to embodiments of the present invention. It can be seen that the mean square value (RMS) of the surface roughness after heat treatment with the multi-cycle water vapor in this application is reduced from 2.38nm to 1.69 nm.
FIG. 4 is the UV spectrophotometer analysis results of ZTO films after general annealing and after multi-cycle rapid water vapor heat treatment in the preparation of zinc tin oxide transparent conductive films according to the example of the present invention. It was found that the transmittance was improved.
FIG. 5 is a graph showing the transfer characteristics of a device after a conventional water vapor annealing and after a multi-cycle rapid water vapor heat treatment in the preparation of a zinc tin oxide transparent conductive film according to an embodiment of the present invention. It can be known that the switching ratio of the device is improved by two orders of magnitude, the sub-threshold swing amplitude is reduced, and the mobility is improved.
The film preparation step will now be specifically described by taking an example of preparing a tungsten zinc tin oxide transparent conductive film on a glass substrate material by a wet method film preparation method.
(1) According to the molar ratio of 0.291:0.679:0.03, tin tetrachloride pentahydrate, zinc acetate dihydrate and tungsten pentachloride are weighed and poured into 50mL of ethylene glycol monomethyl ether solvent in sequence, and then magnetic stirring is carried out. And after the solution is stirred to be clear, uniformly mixed precursor solution with the molar concentration of 0.3mol/L is obtained, and certain monoethanolamine is added to ensure that the molar ratio of the ion concentration in the solution to the monoethanolamine is 1.
(2) The prepared solution is heated in a water bath for 70 ℃ and is kept for 3 hours to form a WZTO solution.
(3) Using a common glass slide as a substrate, respectively carrying out ultrasonic cleaning on the substrate by using analytically pure acetone, alcohol and deionized water to clean the glass substrate, drying, and then spin-coating a tungsten zinc tin oxide solution, wherein the rotating speed of a spin coater is 3000 rpm/s.
(4) And performing pre-annealing after the film is subjected to spin coating, wherein the annealing temperature is 150 ℃, the annealing time is 10 minutes, and the atmosphere is air.
(5) And (3) putting the film sample into a quartz boat in an annealing furnace, heating the film sample to 400 ℃ from room temperature, opening a connection switch of a water vapor generating device, disconnecting the film sample after 10 seconds of connection, keeping the constant temperature of 400 ℃ and drying the film sample for 30 seconds, and then introducing water vapor again for next circulation. The number of the above-mentioned circulation process is 15. FIG. 2 is a schematic diagram of a multi-cycle rapid steam heat treatment cycle according to an embodiment of the present invention, and it can be seen that a cycle of multiple cycles of steam heat treatment is adopted in the present application.
FIG. 6 shows AFM test results for WZTO films after general annealing and after multi-cycle rapid water vapor heat treatment in preparing a W-Zn-Sn oxide transparent conductive film according to an embodiment of the present invention. It can be seen that the RMS of the heat-treated water with the multi-cycle water vapor in this application was reduced from 2.22nm to 1.30 nm.
Fig. 7 shows the results of uv spectrophotometer analysis of WZTO films after general annealing and after multi-cycle rapid water vapor heat treatment when preparing a tungsten zinc tin oxide transparent conductive film according to an embodiment of the present invention. As can be seen from fig. 7, the transmittance is significantly increased.
FIG. 8 is a graph showing the transfer characteristics of devices after conventional annealing and after multi-cycle rapid water vapor thermal treatment when a transparent conductive film of tungsten-zinc-tin oxide is prepared according to an embodiment of the present invention. Referring to fig. 8, it can be seen that the switching ratio of the device is improved by two orders of magnitude, the sub-threshold swing is reduced, and the mobility is improved.
The pre-annealing in the film preparation method can primarily cure the pattern of the film, and reduce the influence of water and oxygen in the air on the performance of the film. Can take place hydrolysis earlier after once only letting in vapor, take place polymerization after the hydrolysis is accomplished, but once hydrolysis can not make whole hydroxyl and water combine, consequently adopt the substep in this application to let in vapor and enable hydrolysis to take place repeatedly, the oxidation is more abundant for the rete is compacter, therefore the surface is more smooth, and roughness reduces, and the device performance also obtains improving.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (4)
1. A method for preparing a thin film by a wet method is characterized by comprising the following steps:
dissolving a solute metal compound in an organic solvent to obtain a precursor solution;
preparing an initial film according to the precursor solution;
carrying out early-stage annealing on the initial film;
after the early-stage annealing is finished, performing cyclic steam heat treatment for specified times to obtain a finished film;
and after the early-stage annealing is finished, performing cyclic steam heat treatment for specified times to obtain a finished film, which specifically comprises the following steps:
putting the annealed initial film on a quartz boat in an annealing furnace, wherein the temperature of the annealing furnace is increased to 400 ℃ from normal temperature;
introducing water vapor into the annealing furnace, wherein the introduction time of the water vapor is kept for 10 s;
the annealing furnace is dried for 30s at the constant temperature of 400 ℃, and then water vapor is introduced again for the next circulation;
and performing 10-15 times of circulation process to obtain a finished product film.
2. The wet method for preparing a thin film according to claim 1, wherein the dissolving the solute metal compound in an organic solvent to obtain a precursor solution specifically comprises:
dissolving the solute metal compound in the organic solvent according to the mixing molar ratio of the solute metal compound to the organic solvent to obtain a mixed solution;
and mixing and stirring the mixed solution, and obtaining a precursor solution after the mixed solution is clarified.
3. The method for preparing a thin film according to claim 1, wherein the preparing an initial thin film according to the precursor solution specifically comprises:
taking a common glass slide as a substrate, and sequentially carrying out ultrasonic cleaning on the substrate by using analytically pure acetone, alcohol and deionized water;
drying the cleaned substrate;
and smearing the dried substrate according to the precursor solution to obtain an initial film.
4. The method for wet-process thin film preparation according to claim 1, wherein the pre-annealing of the initial thin film specifically comprises:
the annealing temperature is 100-200 ℃, the annealing time is 10min, and the atmosphere is air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711236440.7A CN107978513B (en) | 2017-11-30 | 2017-11-30 | Method for preparing film by wet method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711236440.7A CN107978513B (en) | 2017-11-30 | 2017-11-30 | Method for preparing film by wet method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107978513A CN107978513A (en) | 2018-05-01 |
| CN107978513B true CN107978513B (en) | 2019-12-31 |
Family
ID=62008565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711236440.7A Active CN107978513B (en) | 2017-11-30 | 2017-11-30 | Method for preparing film by wet method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107978513B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7199061B2 (en) * | 2003-04-21 | 2007-04-03 | Applied Materials, Inc. | Pecvd silicon oxide thin film deposition |
| CN102244010A (en) * | 2011-06-03 | 2011-11-16 | 桂林电子科技大学 | Preparation method of p-CuAlO2/n-ZnO:Al transparent thin film heterojunction of glass substrate |
| CN105244283A (en) * | 2015-10-26 | 2016-01-13 | 华南理工大学 | Preparation method for UV micro graphical oxide film and film transistor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI348766B (en) * | 2007-10-04 | 2011-09-11 | Taiwan Tft Lcd Ass | Method of fabricating thin film transistor |
-
2017
- 2017-11-30 CN CN201711236440.7A patent/CN107978513B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7199061B2 (en) * | 2003-04-21 | 2007-04-03 | Applied Materials, Inc. | Pecvd silicon oxide thin film deposition |
| CN102244010A (en) * | 2011-06-03 | 2011-11-16 | 桂林电子科技大学 | Preparation method of p-CuAlO2/n-ZnO:Al transparent thin film heterojunction of glass substrate |
| CN105244283A (en) * | 2015-10-26 | 2016-01-13 | 华南理工大学 | Preparation method for UV micro graphical oxide film and film transistor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107978513A (en) | 2018-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105489486B (en) | A kind of preparation method based on the high k dielectric layer thin film transistor (TFT) of ultra-thin magnesia | |
| CN108963001A (en) | A kind of method of located growth perovskite thin film array | |
| CN105575551A (en) | Method of directly preparing flexible and transparent conductive film through sol-gel process | |
| CN106549079A (en) | A kind of ultraviolet light detector and preparation method thereof | |
| CN110034007B (en) | Method for realizing ultrahigh-precision patterning of transparent stretchable electrode | |
| CN102787309B (en) | A kind of aluminum oxide film and preparation method and application thereof | |
| CN104911567B (en) | A kind of method that sol-gal process prepares p-type cuprous oxide thin film material | |
| CN107093640A (en) | A kind of CsPbI of ion doping2Br films, preparation method and applications | |
| CN108321299A (en) | A kind of unleaded perovskite thin film of low-dimensional and its unleaded perovskite preparation method of solar battery | |
| CN108987283A (en) | A kind of gallium tin oxide semiconductor thin film transistor (TFT) and its preparation method and application | |
| CN107978513B (en) | Method for preparing film by wet method | |
| CN108110068A (en) | A kind of unleaded perovskite solar cell and preparation method thereof | |
| CN104086091A (en) | Preparation method of in-situ growth quantum dot optical film | |
| CN105244283B (en) | The preparation method and thin film transistor (TFT) of ultraviolet pattern sull | |
| CN104176944A (en) | Method for modifying OTS self-assembled film on glass substrate | |
| CN108417495A (en) | A kind of preparation of the thin film transistor (TFT) of metal oxide passivation | |
| CN104726851B (en) | A kind of method that sol-gal process prepares p-type SnO 2 thin film material | |
| CN109097757B (en) | Preparation method of praseodymium ion doped hafnium oxide ferroelectric film | |
| CN105256374B (en) | A kind of method that organic perovskite film preparation device prepares CH3NH3PbI3 films | |
| CN102176511B (en) | Preparation method of liquid metal droplet based molecular node | |
| CN105322094A (en) | Preparation method of titanium dioxide thin film for perovskite solar cell | |
| TWI435846B (en) | A method for preparing transparent conductive zinc oxide thin film by dipping stitch doping technique | |
| CN109119547B (en) | A kind of method of glucose reduction preparation p-type stannous oxide thin-film material | |
| CN113078042B (en) | Preparation method of thin film transistor | |
| CN108933079A (en) | A kind of gallium tin oxide semiconductor film and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |