CN114277363A - Film growth method with continuously adjustable optical constant - Google Patents
Film growth method with continuously adjustable optical constant Download PDFInfo
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- CN114277363A CN114277363A CN202111591537.6A CN202111591537A CN114277363A CN 114277363 A CN114277363 A CN 114277363A CN 202111591537 A CN202111591537 A CN 202111591537A CN 114277363 A CN114277363 A CN 114277363A
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Abstract
The invention belongs to the field of film growth, and particularly relates to a film growth method with continuously adjustable optical constants, which comprises the steps of preparing precursor liquid; carrying out surface treatment on the substrate; after the treatment is finished, a layer of uniform liquid film is absorbed and grown on the substrate; placing the substrate for adsorbing and growing a layer of uniform liquid film in a furnace tube with the temperature of 300-400 ℃ for low-temperature heat treatment; in order to improve the efficiency and the film quality, the operations of liquid film growth and low-temperature heat treatment can be repeated after the low-temperature heat treatment is finished, so that a thicker film layer is obtained; then raising the temperature of the furnace tube to 800-1300 ℃ for high-temperature heat treatment, thereby obtaining an optical film with continuously adjustable optical constants; the invention realizes the continuous adjustment of the optical constant by changing the components of the precursor solution, the deposition condition and the heat treatment condition of the film, greatly simplifies the film system structure of the filter film and shortens the process time and the cost.
Description
Technical Field
The invention belongs to the field of film growth, and particularly relates to a film growth method with continuously adjustable optical constants.
Background
Optical films, such as reflective films, antireflection films, optical filters, etc., are important components of optical devices, and have important roles in many application fields, such as lasers, optical communication, medicine, criminal investigation, biochemistry, etc. The optical constants of the optical thin film have a great influence on the design of an optical film system structure, the existing optical thin film is generally formed by overlapping a plurality of layers of films with different optical constants, the number of the layers is generally 10-30, and the number of the layers is as much as 100; and the film layers with different optical constants are made of different materials, the optical constant of the same material is usually influenced by the process method, equipment and process parameters, but the optical constant of the optical film usually fluctuates in a small range. If the growth of the optical film with the optical constant continuously adjustable in a larger range can be realized, the film system structure can be greatly simplified, and the process time is shortened; on the other hand, conventional optical thin films are mostly prepared by PVD methods such as sputtering and electron beam evaporation, and if a chemical solution method is adopted to prepare high-quality optical thin films, the cost can be greatly reduced.
Metal Organic Deposition (MOD) is one of Chemical Solution Deposition (CSD) methods, and has been widely studied as a substitute for vacuum method for preparing ferroelectric and superconducting thin films in recent three decades, and can be used for preparing various electronic thin films of oxides, nitrides and sulfides. The growth temperature is lower, the utilization rate of raw materials is high, a large-area uniform film can be formed, the industrialization is easy, and the method is simpler than a sol-gel method. In the MOD method, metal organic compounds such as carboxylate and acetylacetonate are generally used as a metal source, and the precursor solution thereof has a simple composition and is more stable than the sol-gel method. The MOD method has the greatest advantages of low cost and no need of vacuum equipment, and is generally used for the preparation of high-quality electronic thin films and is less used for the preparation of optical thin films.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for growing a film with continuously adjustable optical constants, comprising the following steps:
s1, carrying out surface treatment on a substrate, and preparing corresponding precursor liquid according to the type of the manufactured optical film;
s2, according to the prepared precursor liquid, adsorbing and growing a layer of uniform liquid film on the substrate after surface treatment;
s3, placing the sample obtained in the step S2 in a furnace tube at the temperature of 300-400 ℃ for low-temperature heat treatment;
s4, judging whether the thickness of the optical film meets the requirement or not after the low-temperature heat treatment is finished, if so, executing a step S5, otherwise, returning to the step S2;
s5, after the low-temperature heat treatment is finished, raising the temperature of the furnace tube to 800-1300 ℃ for high-temperature heat treatment;
and S6, obtaining the optical film with continuously adjustable optical constants after the high-temperature heat treatment is finished.
Further, the precursor solution prepared in step S1 includes a metal organic salt, a thickener, and a solvent, the concentration of the metal atoms in the metal organic salt is in the range of 0.1 to 1.2 mol, the concentration of the metal atoms is adjusted according to the solubility of the metal organic salt, and the greater the solubility of the metal organic salt, the greater the concentration of the metal atoms.
Further, the substrate is made of K9 glass, quartz glass, silicon wafers, functional devices and the like.
Further, the method for adsorbing a liquid film on the substrate obtained in step S1 includes spin coating, spray coating, drawing, screen printing, doctor blading, and the like.
Further, the low-temperature heat treatment time is 5-15 minutes.
Further, the high-temperature heat treatment time is 45-90 minutes.
Furthermore, the optical constant can be continuously adjusted by changing the components of the precursor solution (metal organic salt, thickening agent, solvent and the like), and changing the film deposition condition and the heat treatment condition (temperature interval, heating rate, ventilation type, flow rate and the like).
The invention has the beneficial effects that:
the invention adopts Metal Organic Deposition (MOD) method, prepares corresponding precursor solution according to different film requirements, thereby growing high-quality optical film with continuously adjustable optical constant.
The invention realizes the continuous adjustment of the optical constant by changing the components of the precursor solution, the deposition condition and the heat treatment condition of the film, greatly simplifies the film system structure of the filter film and shortens the process time and the cost.
Drawings
FIG. 1 is a flow chart of the present invention for preparing a thin film.
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.
A method for growing a thin film with continuously adjustable optical constants, as shown in fig. 1, comprising:
s1, carrying out surface treatment on a substrate, and preparing corresponding precursor liquid according to the type of the manufactured optical film;
s2, according to the prepared precursor liquid, adsorbing and growing a layer of uniform liquid film on the substrate after surface treatment;
s3, placing the sample obtained in the step S2 in a furnace tube at the temperature of 300-400 ℃ for low-temperature heat treatment;
s4, judging whether the thickness of the optical film meets the requirement or not after the low-temperature heat treatment is finished, if so, executing a step S5, otherwise, returning to the step S2;
s5, after the low-temperature heat treatment is finished, raising the temperature of the furnace tube to 800-1300 ℃ for high-temperature heat treatment;
and S6, obtaining the high-quality optical film with the specified thickness after the high-temperature heat treatment is finished.
Preferably, the substrate used includes K9 glass, quartz glass, silicon wafer or functional device, etc.;
preferably, before step S1, a precursor solution is prepared, the precursor solution includes a metal organic salt, a thickener, and a solvent, the concentration of the metal atoms in the metal organic salt is in the range of 0.1-1.2 mol, and the concentration of the metal atoms is adjusted according to the solubility of the metal organic salt.
Specifically, the species of the metal atom in the metal organic salt includes titanium, silicon, tantalum, niobium, and the like;
preferably, in step S1, the substrate may be surface-treated by three times of ultrasonic processing, and the substrate is sequentially subjected to ultrasonic processing in acetone, ethanol and deionized water, and the time of the three times of ultrasonic processing is 5-10 minutes.
In one embodiment, high quality TiO with continuously adjustable optical constants is prepared2The process for making the optical film includes:
101. k9 glass or quartz glass is used as a substrate,
102. putting the substrate into acetone for ultrasonic treatment, taking out the substrate after the ultrasonic treatment is finished, putting the substrate into ethanol for ultrasonic treatment, taking out the substrate after the ultrasonic treatment is finished, and putting the substrate into deionized water for ultrasonic treatment;
103. adsorbing and growing a layer of uniform liquid film on the substrate obtained in the step 102;
104. placing the sample obtained in the step 103 in a furnace tube with the temperature of 300-400 ℃ for low-temperature heat treatment;
105. after the low-temperature heat treatment is finished, the temperature of the furnace tube is raised to 800-1300 ℃ for high-temperature heat treatment;
106. and after the high-temperature heat treatment is finished, the optical film with continuously adjustable optical constants is obtained.
Preferably, the precursor solution is prepared using titanium acetylacetonate having a titanium metal atom concentration of 0.1 to 1.2 mol, polyvinyl butyral and propionic acid, the polyvinyl butyral being a thickener, before the substrate is subjected to the ultrasonic treatment.
Preferably, the concentration and the temperature rise rate of the precursor solution are adjusted to change the TiO thin film2When the proportion of the thickener is increased and the temperature rise rate is increased, the titanium oxide film TiO is finally obtained2The larger the porosity of the TiO is, the lower the refractive index of the TiO is, thereby achieving high-quality TiO with continuously adjustable optical constants2And (3) preparing an optical film.
Preferably, the substrate is sequentially subjected to ultrasonic operation in acetone, ethanol and deionized water, and the ultrasonic time ranges from 5 minutes to 10 minutes.
Preferably, a uniform liquid film is adsorbed and grown on the substrate by adopting a spin coating method, a spray coating method, a pulling method, a screen printing method, a doctor blade coating method and the like.
In another embodiment, the substrate with a layer of uniform liquid film is placed in a furnace tube at 300-400 ℃ for low-temperature heat treatment for 5-15 minutes, the solvent is volatilized during the low-temperature heat treatment, and preliminary organic decomposition is carried out.
Preferably, the substrate is subjected to low-temperature heat treatment after adsorbing the growth liquid film, the growth liquid film is adsorbed again on the substrate after the low-temperature heat treatment is completed, and the thickness of the optical thin film is adjusted through the cyclic operation of liquid film growth and low-temperature heat treatment.
Preferably, after the low-temperature heat treatment, the temperature of the furnace tube is raised to 800-1300 ℃, and the object after the low-temperature heat treatment is subjected to high-temperature heat treatment for 45-90 minutes.
In the manufacturing process of the optical film, the continuous adjustment of the optical constant is realized through the change of the components of the precursor solution, the change of the deposition condition of the film and the change of the heat treatment condition, and the optical constant of the film layer is adjusted under different process conditions, so that the required high-quality optical film is prepared.
Specifically, the optical constants of the film layers of the prepared optical film are adjusted by changing the temperature interval of the low-temperature heat treatment.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A method for growing a film with continuously adjustable optical constants is characterized by comprising the following steps:
s1, carrying out surface treatment on a substrate, and preparing corresponding precursor liquid according to the type of the manufactured optical film;
s2, according to the prepared precursor liquid, adsorbing and growing a layer of uniform liquid film on the substrate after surface treatment;
s3, placing the sample obtained in the step S2 in a furnace tube at the temperature of 300-400 ℃ for low-temperature heat treatment;
s4, judging whether the thickness of the optical film meets the requirement or not after the low-temperature heat treatment is finished, if so, executing a step S5, otherwise, returning to the step S2;
s5, after the low-temperature heat treatment is finished, raising the temperature of the furnace tube to 800-1300 ℃ for high-temperature heat treatment;
and S6, obtaining the optical film with continuously adjustable optical constants after the high-temperature heat treatment is finished.
2. The method as claimed in claim 1, wherein the precursor solution prepared in step S1 comprises metal organic salt, thickener and solvent, and the concentration of metal atoms in the metal organic salt is 0.1-1.2 mol.
3. The method for growing a thin film according to claim 1, wherein the substrate used is K9 glass, quartz glass, silicon wafer or functional device.
4. The method for growing a thin film according to claim 1, wherein the method for adsorbing a liquid film on the substrate obtained in step S1 is spin coating, spray coating, czochralski method, screen printing or doctor blading.
5. The method as claimed in claim 1, wherein the low temperature heat treatment time is 5 to 15 minutes.
6. The method for growing a thin film with continuously adjustable optical constants as claimed in claim 1, wherein the high temperature heat treatment time is 45 to 90 minutes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115117179A (en) * | 2022-06-10 | 2022-09-27 | 华中科技大学 | Printable porous optical film and preparation method and application thereof |
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