CN107978513A - A kind of wet method prepares film process - Google Patents
A kind of wet method prepares film process Download PDFInfo
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- CN107978513A CN107978513A CN201711236440.7A CN201711236440A CN107978513A CN 107978513 A CN107978513 A CN 107978513A CN 201711236440 A CN201711236440 A CN 201711236440A CN 107978513 A CN107978513 A CN 107978513A
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- annealing
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- wet method
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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
- H01L21/02365—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
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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
- H01L21/02365—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
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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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02656—Special treatments
- H01L21/02664—Aftertreatments
Abstract
The present invention discloses a kind of wet method and prepares film process, including：Solute metal compound is dissolved in organic solvent, obtains precursor solution；Initial film is prepared according to the precursor solution；Annealing early period is carried out to the initial film；The vapor heat treatment of predetermined number of times circulation is carried out after the completion of annealing early period, obtains finished films.Using the method in the present invention water oxygen rate in steam oxidation annealing process can keep constant, so as to improve the quality of active layer film and insulating layer of thin-film, further lift the performance of thin film transistor (TFT).
Description
Technical field
The present invention relates to annealing field, film process is prepared more particularly to a kind of wet method.
Background technology
In recent years, thin film transistor (TFT) is obtained as liquid crystal display and the switching device of Organic Light Emitting Diode active matrix driving
Extensive research is arrived.Vacuum method prepares thin film transistor (TFT) and has begun to be commercialized, but its manufacturing equipment is expensive, of high cost
Can not meet the needs of inexpensive etc. factor.Therefore, it is necessary to develop the low cost system such as inkjet printing, silk-screen printing, solution spin coating
The method of standby thin film transistor (TFT).But active layer and insulating layer of thin-film prepared by above method is often difficult to stably obtain high thin
The characteristic of film transistor, in view of the above problems, it is that wet method prepares film to control oxygen that can be made annealing treatment by steam oxidation
Defect level and reduction defect level, improve mobility.In addition, existing steam oxidation annealing technology is usually all to be passed directly into
Vapor, oxidizing process is simultaneously insufficient, causes the shortcomings that film surface is coarse, and transmissivity is low.
The content of the invention
The object of the present invention is to provide a kind of wet method to prepare film process, can solve steam oxidation annealing process
In water oxygen rate non-constant, active layer film and insulating layer of thin-film ropy problem.
To achieve the above object, the present invention provides following scheme：
A kind of wet method prepares film process, including：
Solute metal compound is dissolved in organic solvent, obtains precursor solution；
Initial film is prepared according to the precursor solution；
Annealing early period is carried out to the initial film；
The vapor heat treatment of predetermined number of times circulation is carried out after the completion of annealing early period, obtains finished films.
Optionally, it is described that solute metal compound is dissolved in organic solvent, obtain precursor solution and specifically include：
According to the solute metal compound and the mixing molar ratio of the organic solvent, by the solute metal compound
It is dissolved in the organic solvent and obtains mixed solution；
The mixed solution is mixed, is stirred, after mixed solution clarification, obtains precursor solution.
Optionally, it is described to be specifically included according to precursor solution preparation initial film：
Using simple glass slide glass as substrate, the substrate is carried out successively with analysis pure acetone, alcohol and deionized water
Ultrasonic cleaning；
The substrate cleaned is dried；
The substrate after drying is smeared according to the precursor solution, obtains initial film.
Optionally, it is described that initial film progress annealing early period is specifically included：
Annealing temperature is 100~200 DEG C, and annealing time 10min, atmosphere is air.
Optionally, the vapor heat treatment of predetermined number of times circulation is carried out after the completion of annealing early period, obtains finished films
Specifically include：
The initial film after annealing is put on the quartz boat in annealing furnace, the annealing furnace temperature is from room temperature liter
To 400 DEG C；
Vapor is passed through into the annealing furnace, the vapor is passed through time holding 10s；
Vapor is passed through again after 400 DEG C of freeze-day with constant temperature 30s of the annealing furnace holding to be circulated next time；
10~15 cyclic processes are carried out, obtain finished films.
The specific embodiment provided according to the present invention, the invention discloses following technique effect：
Wet method provided by the invention prepares film process and prepares film by the way of multi-cycle multiple step format is passed through vapor,
Oxidation reaction is more abundant, shortens annealing time, reduces active layer and insulating layer of thin-film surface roughness, improves transmission
Rate, device performance and the film quality of preparation；And multi-cycle substep adds vapor, can also regulate and control be passed through by step number
Steam vapour amount.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, drawings in the following description are only some implementations of the present invention
Example, for those of ordinary skill in the art, without having to pay creative labor, can also be according to these attached drawings
Obtain other attached drawings.
Fig. 1 prepares film process flow chart for wet method of the embodiment of the present invention；
Fig. 2 is the quick vapor heat treatment cycle schematic diagram of multi-cycle of the embodiment of the present invention；
It is quick after common annealing and by multi-cycle when Fig. 3 prepares zinc-tin oxide transparent conductive film for the embodiment of the present invention
Atomic force microscope (AFM) test result figure of ZTO films after vapor heat treatment；
It is quick after common annealing and by multi-cycle when Fig. 4 prepares zinc-tin oxide transparent conductive film for the embodiment of the present invention
The analysis result of the ultraviolet specrophotometer of ZTO films after vapor heat treatment；
Fig. 5 is that the embodiment of the present invention is prepared during zinc-tin oxide transparent conductive film after common vapor annealing and multi-cycle
Device transfer characteristic curve after quick vapor heat treatment；
It is fast after common annealing and by multi-cycle when Fig. 6 prepares tungsten oxide zinc-tin transparent conductive film for the embodiment of the present invention
The AFM test results of WZTO films after fast vapor heat treatment；
It is fast after common annealing and by multi-cycle when Fig. 7 prepares tungsten oxide zinc-tin transparent conductive film for the embodiment of the present invention
The analysis result of the ultraviolet specrophotometer of WZTO films after fast vapor heat treatment；
It is fast after common annealing and by multi-cycle when Fig. 8 prepares tungsten oxide zinc-tin transparent conductive film for the embodiment of the present invention
Device transfer characteristic curve after fast vapor heat treatment.
Embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other without making creative work
Embodiment, belongs to the scope of protection of the invention.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, it is below in conjunction with the accompanying drawings and specific real
Applying mode, the present invention is described in further detail.
Fig. 1 prepares film process flow chart for wet method of the embodiment of the present invention.Referring to Fig. 1, a kind of wet method prepares film process,
Including：
Step 101：Solute metal compound is dissolved in organic solvent, obtains precursor solution；
Step 102：Initial film is prepared according to the precursor solution；
Step 103：Annealing early period is carried out to the initial film；
Step 104：The vapor heat treatment of predetermined number of times circulation is carried out after the completion of annealing early period, obtains finished films.
Now have to be prepared using wet method exemplified by membrane process prepares zinc-tin oxide transparent conductive film in glass substrate material
Body illustrates operating procedure.
(1) it is 3 by the molar ratio of tin, zinc:7 weigh Tin tetrachloride pentahydrate, and Zinc diacetate dihydrate pours into 50mL's successively
In ethylene glycol monomethyl ether solvent, magnetic agitation is then carried out.After above-mentioned solution stirs to clarify, obtaining molar concentration is
The uniformly mixed precursor solution of 0.3mol/L, adds certain monoethanolamine, makes effects of ion concentration and monoethanolamine
Molar ratio be 1.
(2) by the precursor solution configured carry out 70 DEG C of heating water bath, keep 3 it is small when after formed ZTO solution.
(3) simple glass slide glass is used to be carried out respectively with analysis pure acetone, alcohol and deionized water to substrate as substrate
Ultrasonic cleaning, cleans glass substrate, and inkjet printing zinc-tin oxide solution patterns initial film after drying.
(4) preannealing is carried out after the completion of initial film printing, annealing temperature is 150 DEG C, and annealing time is 10 minutes, atmosphere
For air.
(5) quartz boat being put into initial film in annealing furnace, annealing furnace temperature rise to 400 DEG C from room temperature, open and water
The connecting valve of steam generating device, disconnects after connecting 10s, and vapor progress is passed through again after keeping 400 DEG C of freeze-day with constant temperature 30s
Circulate next time.Above-mentioned cyclic process number is 12 times.Fig. 2 is the quick vapor heat treatment cycle of multi-cycle of the embodiment of the present invention
Schematic diagram, it is seen then that the cycle of the multiple recirculated water steam-heated procedure of use in the application.
Pass through multi-cycle with above-mentioned after common annealing when Fig. 3 prepares zinc-tin oxide transparent conductive film for the embodiment of the present invention
The AFM test result figures of ZTO films after quick vapor heat treatment.As it can be seen that using the multi-cycle vapor heat in the application
Surface roughness mean-square value (RMS) after processing is reduced to 1.69nm by 2.38nm.
It is quick after common annealing and by multi-cycle when Fig. 4 prepares zinc-tin oxide transparent conductive film for the embodiment of the present invention
The analysis result of the ultraviolet specrophotometer of ZTO films after vapor heat treatment.Understand, transmitance increases.
Fig. 5 is that the embodiment of the present invention is prepared during zinc-tin oxide transparent conductive film after common vapor annealing and multi-cycle
Device transfer characteristic curve after quick vapor heat treatment.Understand, devices switch is than improving two orders of magnitude, subthreshold swing
Decline, mobility improves.
Now exemplified by membrane process being prepared using wet method tungsten oxide zinc-tin transparent conductive film is prepared in glass substrate material
Illustrate film preparation step.
(1) it is 0.291 by the molar ratio of tin, zinc, tungsten:0.679:0.03 weighs Tin tetrachloride pentahydrate, two hydration acetic acid
Zinc, tungsten pentachloride pour into the ethylene glycol monomethyl ether solvent of 50mL successively, then carry out magnetic agitation.Treat that above-mentioned solution is stirred to clear
After clear, the uniformly mixed precursor solution that molar concentration is 0.3mol/L is obtained, certain monoethanolamine is added, makes in solution
The molar ratio of ion concentration and monoethanolamine is 1.
(2) by the solution configured carry out 70 DEG C of heating water bath, keep 3 it is small when after formed WZTO solution.
(3) simple glass slide glass is used to be carried out respectively with analysis pure acetone, alcohol and deionized water to substrate as substrate
Ultrasonic cleaning, cleans glass substrate, spin coating tungsten oxide zinc-tin solution after drying, spin coating machine speed 3000rpm/s.
(4) preannealing is carried out after the completion of film spin coating, annealing temperature is 150 DEG C, and annealing time is 10 minutes, and atmosphere is sky
Gas.
(5) quartz boat being put into film sample in annealing furnace, rises to 400 DEG C, opening is filled with vapor from room temperature
The connecting valve put, disconnects after connecting 10s, and be passed through vapor again after 400 DEG C of freeze-day with constant temperature 30s of holding is followed next time
Ring.Above-mentioned cyclic process number is 15 times.Fig. 2 is the quick vapor heat treatment cycle schematic diagram of multi-cycle of the embodiment of the present invention,
As it can be seen that the cycle of the multiple recirculated water steam-heated procedure of use in the application.
It is fast after common annealing and by multi-cycle when Fig. 6 prepares tungsten oxide zinc-tin transparent conductive film for the embodiment of the present invention
The AFM test results of WZTO films after fast vapor heat treatment.As it can be seen that it is heat-treated using the multi-cycle vapor in the application
RMS afterwards is reduced to 1.30nm by 2.22nm.
It is fast after common annealing and by multi-cycle when Fig. 7 prepares tungsten oxide zinc-tin transparent conductive film for the embodiment of the present invention
The analysis result of the ultraviolet specrophotometer of WZTO films after fast vapor heat treatment.According to Fig. 7, transmitance substantially carries
Rise.
It is fast after common annealing and by multi-cycle when Fig. 8 prepares tungsten oxide zinc-tin transparent conductive film for the embodiment of the present invention
Device transfer characteristic curve after fast vapor heat treatment.According to Fig. 8, devices switch is than improving two orders of magnitude, subthreshold
It is worth the amplitude of oscillation to decline, mobility improves.
Preannealing in above-mentioned method for manufacturing thin film can make film primary solidification pattern, reduce the water oxygen in air to its property
The influence of energy.Afterwards hydrolysis can first occur for the disposable vapor that is passed through, and polymerisation can occur after the completion of hydrolysis, but
It is that a hydrolysis can not be such that whole hydroxyls are combined with water, therefore be passed through vapor using the substep in the application to make
Hydrolysis repeated, and oxidation is more abundant so that film layer is finer and close, therefore surface is more smooth, and roughness reduces, device
Part performance is also improved.
Each embodiment is described by the way of progressive in this specification, what each embodiment stressed be and other
The difference of embodiment, between each embodiment identical similar portion mutually referring to.
Specific case used herein is set forth the principle of the present invention and embodiment, and above example is said
It is bright to be only intended to help the method and its core concept for understanding the present invention；Meanwhile for those of ordinary skill in the art, foundation
The thought of the present invention, in specific embodiments and applications there will be changes.In conclusion this specification content is not
It is interpreted as limitation of the present invention.
Claims (5)
1. a kind of wet method prepares film process, it is characterised in that including：
Solute metal compound is dissolved in organic solvent, obtains precursor solution；
Initial film is prepared according to the precursor solution；
Annealing early period is carried out to the initial film；
The vapor heat treatment of predetermined number of times circulation is carried out after the completion of annealing early period, obtains finished films.
2. wet method according to claim 1 prepares film process, it is characterised in that described to dissolve solute metal compound
In organic solvent, precursor solution is obtained, is specifically included：
According to the solute metal compound and the mixing molar ratio of the organic solvent, the solute metal compound is dissolved
Mixed solution is obtained in the organic solvent；
The mixed solution is mixed, is stirred, after mixed solution clarification, obtains precursor solution.
3. wet method according to claim 1 prepares film process, it is characterised in that described according to the precursor solution system
Standby initial film, specifically includes：
Using simple glass slide glass as substrate, ultrasound is carried out to the substrate successively with analysis pure acetone, alcohol and deionized water
Ripple cleans；
The substrate cleaned is dried；
The substrate after drying is smeared according to the precursor solution, obtains initial film.
4. wet method according to claim 1 prepares film process, it is characterised in that before the progress to the initial film
Phase anneals, and specifically includes：
Annealing temperature is 100~200 DEG C, and annealing time 10min, atmosphere is air.
5. wet method according to claim 1 prepares film process, it is characterised in that is referred to after the completion of annealing early period
Determine the vapor heat treatment of number of cycles, obtain finished films, specifically include：
The initial film after annealing is put on the quartz boat in annealing furnace, the annealing furnace temperature rises to from room temperature
400℃；
Vapor is passed through into the annealing furnace, the vapor is passed through time holding 10s；
Vapor is passed through again after 400 DEG C of freeze-day with constant temperature 30s of the annealing furnace holding to be circulated next time；
10~15 cyclic processes are carried out, obtain finished films.
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| CN201711236440.7A CN107978513B (en) | 2017-11-30 | 2017-11-30 | Method for preparing film by wet method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711236440.7A CN107978513B (en) | 2017-11-30 | 2017-11-30 | Method for preparing film by wet method |
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| CN107978513B CN107978513B (en) | 2019-12-31 |
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Citations (4)
| 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 |
| US20090093093A1 (en) * | 2007-10-04 | 2009-04-09 | Taiwan Tft Lcd Association | Method of fabricating thin film transistor |
| 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 |
-
2017
- 2017-11-30 CN CN201711236440.7A patent/CN107978513B/en active Active
Patent Citations (4)
| 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 |
| US20090093093A1 (en) * | 2007-10-04 | 2009-04-09 | Taiwan Tft Lcd Association | Method of fabricating thin film transistor |
| 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 |
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