CN113235048A - Nanocrystalline titanium dioxide functional film and preparation method thereof - Google Patents

Nanocrystalline titanium dioxide functional film and preparation method thereof Download PDF

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CN113235048A
CN113235048A CN202110484165.0A CN202110484165A CN113235048A CN 113235048 A CN113235048 A CN 113235048A CN 202110484165 A CN202110484165 A CN 202110484165A CN 113235048 A CN113235048 A CN 113235048A
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titanium dioxide
film
film layer
grain growth
layer
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薄铁柱
刘辉
马婧
杨金慧
李庆
蔡华
廉姣
王辰
刘畅
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China Building Materials Academy CBMA
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Abstract

The invention relates to a nanocrystalline titanium dioxide functional film and a preparation method thereof. The nanocrystalline titanium dioxide functional film comprises titanium dioxide film layers and grain growth inhibiting film layers which are alternately stacked, wherein the grain growth inhibiting film layers are metal oxide layers with amorphous structures, and the thickness of the grain growth inhibiting film layers is 0.5-1.5 nm. The invention introduces the crystal grain growth inhibiting film layer into the titanium dioxide film to play a role of a crystal grain growth inhibitor, can effectively control the growth of the titanium dioxide crystal grains, controls the crystal grain size of the titanium dioxide within a set range, simultaneously has lower proportion of the crystal grain growth inhibiting film layer in the whole film structure, has little influence on the performance of the titanium dioxide film, and can exert the performance advantage of the titanium dioxide film to the maximum extent.

Description

Nanocrystalline titanium dioxide functional film and preparation method thereof
Technical Field
The invention relates to the technical field of photoelectric functional films, in particular to a nanocrystalline titanium dioxide functional film and a preparation method thereof.
Background
The titanium dioxide film has the advantages of excellent visible light transparency, good thermal stability and chemical stability, wide forbidden band, high refractive index, no toxicity and the like, is a functional film material which attracts attention, and can be widely applied to the fields of photocatalysts, ultraviolet detection, thermosensitive materials, solar cells, film optical waveguides, gas sensors and the like. Titanium dioxide has three structures in nature, namely rutile phase (r-TiO)2) Anatase phase (a-TiO)2) And brookite phase (b-TiO)2). TiO of different crystal forms2The optical band gap values of (a) are all larger than 3.0eV, so that the optical band gap has good light transmission in a visible light wave band.
The anatase titanium dioxide has larger specific surface area, stronger adsorption capacity to oxygen and higher carrier mobility than the rutile phase, thereby having higher photocatalytic activity. In addition, the anatase type titanium dioxide has a forbidden bandwidth similar to that of GaN, ZnO and SiC, and a refractive index matched with that of GaN, so that the reflectivity of an interface can be greatly reduced, the performance of a photoelectric device is improved, and the anatase type titanium dioxide has high carrier mobility and is a promising transparent photoelectric thin film material.
In order to produce anatase titanium dioxide thin films, a higher deposition temperature is generally required or annealing is used to convert the structure of titanium dioxide from an amorphous state to anatase. However, the sizes of the titanium dioxide grains cannot be controlled by the two treatment modes, and abnormal growth of the titanium dioxide film grains is often caused. Along with the growth of crystal grains, the scattering and absorption of crystal boundaries are enhanced, so that the extinction coefficient of the titanium dioxide film is increased, the transmittance of the film is greatly reduced, and the application of the anatase type titanium dioxide functional film is severely restricted.
Disclosure of Invention
The invention mainly aims to provide a nanocrystalline titanium dioxide functional film and a preparation method thereof, so as to solve the technical problems of low transmittance and the like caused by crystal grain growth in the preparation process of the titanium dioxide film.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. According to the invention, the nanocrystalline titanium dioxide functional film comprises: the titanium dioxide film layers and the grain growth inhibiting film layers are alternately stacked, the grain growth inhibiting film layers are metal oxide layers with amorphous structures, and the thickness of the grain growth inhibiting film layers is 0.5-1.5 nm.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the nanocrystalline titanium dioxide functional thin film is a nanocrystalline titanium dioxide functional thin film, wherein the amorphous metal oxide is aluminum oxide or hafnium oxide.
Preferably, the nanocrystalline titanium dioxide functional film is characterized in that the extinction coefficient of the grain growth suppression film layer in the visible light range is 0.
Preferably, the nanocrystalline titanium dioxide functional thin film is provided, wherein the crystal structure of the titanium dioxide film layer is anatase; the thickness of the titanium dioxide film layer is 5-30 nm.
Preferably, in the nanocrystalline titanium dioxide functional film, the number of the titanium dioxide film layers is at least two, and the thicknesses of all the titanium dioxide film layers are the same.
Preferably, the ratio of the thickness of the grain growth inhibition film layer to the thickness of the titanium dioxide film layer is 1: 3-1: 10.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The preparation method of the nanocrystalline titanium dioxide functional film provided by the invention comprises the following steps: providing a substrate;
alternately depositing a titanium dioxide film layer and a grain growth inhibiting film layer on the substrate, wherein the grain growth inhibiting film layer is a metal oxide layer with an amorphous structure, and the thickness of the grain growth inhibiting film layer is 0.5-1.5 nm;
the deposition method comprises a chemical vapor deposition method, a magnetron sputtering method or an atomic layer deposition method.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, in the preparation method, the method for preparing the nanocrystalline titanium dioxide functional film by using the atomic layer deposition method includes the following steps:
(1) providing a substrate;
(2) designing the total thickness of the nanocrystalline titanium dioxide functional film, the thickness of each titanium dioxide film layer and the material and thickness of each crystal grain growth inhibition film layer according to requirements;
(3) determining the deposition temperature, the deposition rate of the titanium dioxide film layer, the deposition rate of the grain growth inhibition film layer, the sub-cycle times N of the titanium dioxide film layer, the sub-cycle times m of the grain growth inhibition film layer and the total cycle times N; and with H2O is used as an oxygen source, inert gas is used as carrier gas and purge gas, and an atomic layer deposition method is adopted for deposition;
(4) introducing a titanium source into the ALD vacuum chamber at the deposition temperature, wherein the cycle number is n, and obtaining a titanium dioxide film layer;
(5) introducing an aluminum source or a hafnium source into the ALD vacuum chamber at the deposition temperature, wherein the cycle number is m, and obtaining a crystal grain production inhibition layer;
(6) and (5) repeating the step (4) and the step (5) for N times to obtain the nanocrystalline titanium dioxide functional film with the grain growth inhibition film layer structure.
Preferably, the above production method, wherein the titanium source is titanium tetrachloride; the aluminum source is trimethyl aluminum; the hafnium source is tetra (methylethylamine) hafnium or tetra (dimethylamine) hafnium.
Preferably, in the preparation method, the deposition temperature is 200 ℃ to 350 ℃, and the crystal structure of the titanium dioxide thin film layer is anatase.
By the technical scheme, the nanocrystalline titanium dioxide functional film and the preparation method thereof provided by the invention at least have the following advantages:
1. the nanocrystalline titanium dioxide functional film provided by the invention comprises titanium dioxide film layers and grain growth inhibition film layers which are alternately stacked, the grain growth inhibition film layers are limited to be metal oxide layers with amorphous structures, and the thickness of the grain growth inhibition film layers is 0.5-1.5 nm. The invention introduces the crystal grain growth inhibiting film layer into the titanium dioxide film, so that the crystal grain size of the titanium dioxide can be controlled within a set range, and simultaneously, the crystal grain growth inhibiting film layer has lower proportion in the whole film structure, thereby having little influence on the optical performance of the titanium dioxide film and exerting the optical performance advantage of the titanium dioxide film to the maximum extent.
2. The method provided by the invention is characterized in that the titanium dioxide film with the periodic alternating structure is formed by introducing the grain growth inhibiting film layer into the titanium dioxide film and alternately depositing the grain growth inhibiting film layer and the titanium dioxide film layer. In the nanocrystalline titanium dioxide functional film prepared by the method, the titanium dioxide film layer has an anatase crystal structure, and the grain growth inhibition film layers are alternately deposited in the titanium dioxide film layer to play a role of a grain growth inhibitor and effectively control the growth of titanium dioxide grains. Compared with the titanium dioxide film prepared by the common method, the nanocrystalline titanium dioxide functional film prepared by the method has lower extinction coefficient and higher visible light transmittance.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a schematic structural diagram of a nanocrystalline titanium dioxide functional film according to an embodiment of the present invention; wherein 10 is a titanium dioxide film layer, 20 is a crystal grain growth inhibiting film layer, and 30 is a substrate;
fig. 2 shows a graph comparing the transmittance of the nanocrystalline titanium dioxide functional thin film obtained in examples 1 and 2 of the present invention with that of the conventional titanium dioxide thin film, respectively.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to the specific embodiments, structures, characteristics and effects of the nanocrystalline titanium dioxide functional thin film and the preparation method thereof according to the present invention with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
As shown in fig. 1, one embodiment of the present invention provides a nanocrystalline titanium dioxide functional film, which includes: the titanium dioxide film layers 10 and the grain growth inhibiting film layers 20 are alternately stacked, the grain growth inhibiting film layers 20 are metal oxide layers with amorphous structures, and the thickness of the grain growth inhibiting film layers 20 is 0.5-1.5 nm.
The grain growth inhibiting film layer of the present embodiment has an amorphous structure, and the optical performance of the grain growth inhibiting film layer does not change due to the change of the thickness, and the grain growth inhibiting film layer is required to have a high transmittance characteristic within the operating wavelength so as not to affect the optical performance of the titanium dioxide film layer.
The grain growth inhibition film layer is preferably controlled within 1.5nm as the thickness is thinner under the condition of ensuring that the film layer is uniform, continuous and free of defects. The grain growth inhibiting layer is not required to be too thick, and if the grain growth inhibiting layer is too thick, the proportion of the grain growth inhibiting layer is large, so that the optical performance of the titanium dioxide film layer is influenced, and therefore, the thinner the grain growth inhibiting layer is, the better the thickness of the grain growth inhibiting layer is on the premise of inhibiting the growth of titanium dioxide grains is.
In the embodiment, the grain growth inhibition film layer is introduced into the titanium dioxide film, and the titanium dioxide film with a periodic alternate structure is formed in a mode of alternately depositing the titanium dioxide film layer and the grain growth inhibition film layer; according to the film design of the present embodiment, the grain size of the titanium dioxide can be controlled within a predetermined range.
In the embodiment, the grain growth inhibition film layer which is a metal oxide layer with an amorphous structure is introduced into the titanium dioxide film, and can play a role of a grain growth inhibitor in the process of preparing the film layer, so that the growth of titanium dioxide grains in the titanium dioxide film layer can be effectively controlled, and the refractive index of the titanium dioxide film layer is controlled within a set range. On the premise of ensuring that the grain growth inhibition film layer achieves the inhibition effect, the thinner the grain growth inhibition film layer is, the better the grain growth inhibition film layer is, meanwhile, the grain growth inhibition film layer accounts for a lower proportion in the whole film structure, has little influence on the performance (especially the optical performance) of the titanium dioxide film, and can exert the performance advantage of the titanium dioxide film to the greatest extent.
On the premise that the thickness of the grain growth inhibition film layer can limit the growth of the titanium dioxide film layer, the thickness of the grain growth inhibition film layer is not specifically limited in the embodiment, the thinner the grain growth inhibition film layer is, the better the grain growth inhibition film layer can limit the growth of the crystal grain, at present, the thickness of the grain growth inhibition film layer needs to be obtained through experiments, experiments prove that, for the titanium dioxide film layer, the growth of the crystal grain in the titanium dioxide film layer can be controlled only when the thickness of the corresponding grain growth inhibition film layer is larger than 1 nanometer, and the limitation is not limited when the thickness is smaller than 1 nanometer. However, the thickness of the grain growth inhibiting film layer is not necessarily as thick as possible, and too thick may affect the optical properties of the titanium dioxide film layer, and therefore, experiments are required to determine the thickness meeting the requirements.
In some embodiments, the amorphous structure isThe metal oxide is aluminum oxide (Al)2O3) Or hafnium oxide (HfO)2)。
In some embodiments, the grain growth inhibiting film layer 20 has an extinction coefficient of 0 in the visible range.
The embodiment limits that the grain growth inhibition film layer has no light absorption in the working wavelength range, otherwise, the transmittance of the titanium dioxide film is reduced, and the optical performance of the titanium dioxide film is further influenced.
In some preferred embodiments, the titanium dioxide film layer has an anatase-type crystal structure; the thickness of the titanium dioxide film layer is 5-30 nm. In some embodiments, the number of titanium dioxide film layers is at least two, and all titanium dioxide film layers have the same thickness.
In some embodiments, the ratio of the thickness of the grain growth inhibiting film layer 20 to the thickness of the titanium dioxide film layer 10 is 1:3 to 1: 10.
In some preferred embodiments, the ratio of the thickness of the grain growth inhibiting film layer 20 to the thickness of the titanium dioxide film layer 10 is 1:5, and the thickness of the grain growth inhibiting film layer is 0.8 mm.
Another embodiment of the present invention further provides a method for preparing a nanocrystalline titanium dioxide functional film, which specifically comprises the following steps:
providing a substrate;
alternately depositing a titanium dioxide film layer and a grain growth inhibiting film layer on the substrate, wherein the grain growth inhibiting film layer is a metal oxide layer with an amorphous structure, and the thickness of the grain growth inhibiting film layer is 0.5-1.5 nm;
the deposition method comprises a chemical vapor deposition method, a magnetron sputtering method or an atomic layer deposition method.
The nanocrystalline titanium dioxide functional film can be prepared by a chemical vapor deposition method, a magnetron sputtering method, an atomic layer deposition method and other film coating methods which can accurately control the film thickness and the titanium dioxide crystal structure. The Atomic Layer Deposition (ALD) technology with self-limiting and layered growth, high controllability of deposition parameters, excellent deposition uniformity, conformality and consistency is preferably adopted as the preparation method of the nanocrystalline titanium dioxide functional thin film.
Further, the method for preparing the nanocrystalline titanium dioxide functional film by adopting the atomic layer deposition method comprises the following steps:
(1) providing a substrate;
(2) designing the total thickness of the nanocrystalline titanium dioxide functional film, the thickness of each titanium dioxide film layer and the material and thickness of each crystal grain growth inhibition film layer according to requirements;
(3) determining the deposition temperature, the deposition rate of the titanium dioxide film layer, the deposition rate of the grain growth inhibition film layer, the sub-cycle times N of the titanium dioxide film layer, the sub-cycle times m of the grain growth inhibition film layer and the total cycle times N; and with H2O as an oxygen source, with an inert gas, e.g. N2Depositing by adopting an atomic layer deposition method as carrier gas and purge gas;
in this step, the deposition rate of the titanium dioxide film and the deposition rate of the grain growth inhibition film are firstly measured under the same deposition conditions, then the sub-cycle number of each film is calculated according to the designed film thickness, and then the total cycle number is calculated according to the designed total thickness of the nanocrystalline titanium dioxide functional film.
(4) Introducing a titanium source into the ALD vacuum chamber at the deposition temperature, wherein the cycle number is n, and obtaining a titanium dioxide film layer;
specifically, a purge gas, such as N, is introduced into the ALD vacuum chamber2And the concentration thereof is brought to a standard value, according to the pulse time of the aluminum source or the hafnium source, H2The pulse time of the O source; alternately introducing an aluminum source or a hafnium source and H into a vacuum chamber at a deposition temperature2O source, cycle number m, to deposit a thickness of m GPC(aluminum oxide or hafnium oxide)The grain production inhibiting layer of (1);
(5) introducing an aluminum source or a hafnium source into the ALD vacuum chamber at the deposition temperature, wherein the cycle number is m, and obtaining a crystal grain production inhibition layer;
in particular, according to the pulse time of the titanium source, H2The pulse time of the O source is alternated into the vacuum chamber at the deposition temperatureIntroducing a titanium source H2O source, cycle number n, to deposit a thickness of nxGPC(titanium dioxide)The titanium dioxide film layer;
(6) and (5) repeating the step (4) and the step (5) for N times, and finally preparing the nanocrystalline titanium dioxide functional film with the grain growth inhibition film layer structure.
In some embodiments, the titanium source is titanium tetrachloride; the aluminum source is trimethyl aluminum; the hafnium source is tetra (methylethylamine) hafnium or tetra (dimethylamine) hafnium.
In some embodiments, the deposition temperature is 200 ℃ to 350 ℃, and the crystal structure of the titanium dioxide thin film layer is anatase.
The nanocrystalline titanium dioxide functional film prepared by the method comprises titanium dioxide film layers and grain growth inhibiting film layers which are alternately stacked, wherein the titanium dioxide film layers have an anatase crystal structure, and the grain growth inhibiting film layers (aluminum oxide layers or hafnium oxide layers) play a role of grain growth inhibitors and can effectively control the growth of titanium dioxide grains. Compared with the titanium dioxide film prepared by the common method, the nanocrystalline titanium dioxide functional film prepared by the method has lower extinction coefficient and higher visible light transmittance.
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with certain insubstantial modifications and adaptations of the invention based on the teachings of the invention set forth herein.
In the following examples of the present invention, all reagents used are commercially available unless otherwise specified, and the methods involved are conventional unless otherwise specified.
In the following examples of the present invention, the components referred to are all commercially available products well known to those skilled in the art unless otherwise specified.
Example 1
A nanocrystalline titanium dioxide functional film, comprising: titanium dioxide film layer and Al2O3The thickness of the titanium dioxide film layer is 5.4nm, and the thickness of the grain growth inhibition film layer is 0.66 nm.
The preparation method of the nanocrystalline titanium dioxide functional film comprises the following steps:
the preparation method of the nanocrystalline titanium dioxide functional film by the ALD technology comprises the following specific processes and parameters:
(1) selection of precursor materials: using trimethylaluminum as Al2O3Precursor material of film layer, titanium tetrachloride as TiO2Precursor material of film layer with H2O as oxygen source of film material and N2As carrier and purge gases;
(2) selection of deposition temperature: the deposition temperature of the ALD deposited titanium dioxide thin film is 200 ℃;
(3) determining the deposition rates of the grain growth inhibition film layer and the titanium dioxide film layer: al is measured at a deposition temperature of 200 deg.C2O3The deposition rate of the film is 0.110nm/cycle, TiO2The deposition rate of the film is 0.054 nm/cycle;
(4) determination of the number of subcycles: according to Al2O3Layer and TiO2The thickness ratio of the layers was 0.66 nm: 5.4nm of structural design, and calculating to obtain Al2O3Number of layer subcycles m 6 cycles, TiO2The number n of sub-cycles of a layer is 100 cycles; the total thickness of the film layer in each period is 6.06 nm;
(5) determination of the total number of cycles: setting the total thickness of the nanocrystalline titanium dioxide functional film to be 400nm, and calculating the total cycle number N to be 66 cycles according to the film thickness value (6.06nm) of each period;
(6) setting the program of the ALD process according to the deposition temperature, the sub-cycle times, the total cycle times and other process parameters;
(7) introducing a cleaning gas N into the ALD vacuum chamber2And the concentration reaches the standard value, the pulse time of the trimethylaluminum is set to be 5s, H2The pulse time of O is 5 s; introducing trimethyl aluminum and H alternately into the vacuum chamber at 200 DEG C2O, cycle number m 6cycle, deposition of Al2O3A layer;
(8) setting the pulse time of titanium tetrachloride to be 10s, H2The pulse time of O is 10 s; alternately introducing titanium tetrachloride and H into the vacuum chamber at 200 DEG C2O, cycle number n 100 cycles, deposit TiO2A layer;
(9) repeating the processes (7) and (8) for the number of times of N ═ 66 cycles, and finally preparing the nanocrystalline titanium dioxide functional film with the thickness of 400 nm.
In the nano-crystalline titanium dioxide functional thin film prepared in the embodiment 1, the crystal structure of titanium dioxide is anatase type, the crystal grain size is less than or equal to 5nm, and the light transmittance in the wavelength range of 300nm to 1000nm is shown in fig. 2, as can be seen from fig. 2, the TiO prepared in the embodiment 1 of the invention2-Al2O3The film had an average light transmission of about 70%.
Example 2:
a nanocrystalline titanium dioxide functional film, comprising: titanium dioxide film layer and HfO2The thickness of the titanium dioxide film layer is 8.55nm, and the thickness of the grain growth inhibition film layer is 1.2 nm.
The preparation method of the nanocrystalline titanium dioxide functional film comprises the following steps:
the preparation method of the nanocrystalline titanium dioxide functional film by the ALD technology comprises the following specific processes and parameters:
(1) selection of precursor materials: using hafnium tetra (dimethylamine) as HfO2Precursor material of film layer, titanium tetrachloride as TiO2Precursor material of film layer with H2O as oxygen source of film material and N2As carrier and purge gases;
(2) selection of deposition temperature: the deposition temperature of the ALD deposited titanium dioxide thin film is 250 ℃;
(3) determining the deposition rates of the grain growth inhibition film layer and the titanium dioxide film layer: determination of HfO at a deposition temperature of 250 deg.C2The deposition rate of the film is 0.08nm/cycle, TiO2The deposition rate of the film is 0.057 nm/cycle;
(4) determination of the number of subcyclesDetermining: according to HfO2Layer and TiO2The thickness ratio of the layers was 1.2 nm: 8.55nm of structure design, and calculating to obtain HfO2Number of layer subcycles m 15 cycles, TiO2The number of sub-cycles of a layer n is 150 cycles. The total thickness of each period film layer is 9.75 nm;
(5) determination of the total number of cycles: setting the total thickness of the nanocrystalline titanium dioxide functional film to be 400nm, and calculating the total cycle number N to be 41 cycles according to the film thickness value (9.75nm) of each period;
(6) setting the program of the ALD process according to the deposition temperature, the sub-cycle times, the total cycle times and other process parameters;
(7) introducing a cleaning gas N into the ALD vacuum chamber2And the concentration thereof was adjusted to a standard value, and the pulse time of hafnium tetra (dimethylamine) was set to 8s, H2The pulse time of O is 8 s; alternately introducing hafnium tetra (dimethylamine) and H into a vacuum chamber at 250 DEG C2O, cycle number m is 15 cycles, deposit HfO2A layer;
(8) the pulse time of titanium tetrachloride is set to be 12s, H2The pulse time of O is 12s, titanium tetrachloride and H are alternately introduced into the vacuum chamber at 250 DEG C2O, cycle number n 150 cycles, deposit TiO2A layer;
(9) repeating the processes (7) and (8) for 41 cycles, and finally preparing the nanocrystalline titanium dioxide functional film with the thickness of 400 nm.
In the nanocrystalline titanium dioxide functional thin film prepared in the embodiment 2, the crystal structure of titanium dioxide is anatase type, the crystal grain size is less than or equal to 8nm, and the transmittance of the nanocrystalline titanium dioxide functional thin film in the wavelength range of 300nm to 1000nm is shown in fig. 2, as can be seen from fig. 2, the TiO prepared in the embodiment 2 of the invention2-HfO2The film had an average light transmission of about 72%.
Comparative example
With titanium tetrachloride being TiO2Precursor material of film layer with H2O as oxygen source of film material and N2As carrier and purge gases; the ALD technique was used to prepare a 400nm titanium dioxide thin film, and comparative example 1 contained no titanium dioxide as compared to example 1Al2O3The grain growth inhibiting film layer, the other corresponding preparation parameters were the same as in example 1.
In the titanium dioxide thin film prepared in the comparative example, the crystal structure of titanium dioxide was anatase type, the crystal grain size was about 30 to 50nm, and the light transmittance thereof in the wavelength range of 300nm to 1000nm was as shown in FIG. 2, as can be seen from FIG. 2, in the wavelength range of 300nm to 1000nm, TiO of the comparative example2The light transmittance of the film was about 65%.
As can be seen from the above, TiO of comparative example2Compared with the thin film, the nanocrystalline titanium dioxide functional thin film obtained in the embodiment 1 and the embodiment 2 has higher light transmittance.
In the description of the present invention, it should be noted that the terms "upper", "lower", "horizontal", "vertical", and the like indicate orientations or positional relationships based on methods or positional relationships shown in the drawings, and are only for convenience of describing the present invention and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A nanocrystalline titanium dioxide functional film, comprising: the titanium dioxide film layers and the grain growth inhibiting film layers are alternately stacked, the grain growth inhibiting film layers are metal oxide layers with amorphous structures, and the thickness of the grain growth inhibiting film layers is 0.5-1.5 nm.
2. The nanocrystalline titanium dioxide functional film according to claim 1,
the metal oxide with the amorphous structure is aluminum oxide or hafnium oxide.
3. The nanocrystalline titanium dioxide functional film according to claim 1,
the extinction coefficient of the grain growth inhibiting film layer in a visible light range is 0.
4. The nanocrystalline titanium dioxide functional film according to claim 1,
the crystal structure of the titanium dioxide film layer is anatase type;
the thickness of the titanium dioxide film layer is 5-30 nm.
5. The nanocrystalline titanium dioxide functional film according to claim 1,
the number of the titanium dioxide film layers is at least two, and the thicknesses of all the titanium dioxide film layers are the same.
6. The nanocrystalline titanium dioxide functional film according to claim 1,
the ratio of the thickness of the grain growth inhibition film layer to the thickness of the titanium dioxide film layer is 1: 3-1: 10.
7. A method for preparing a nanocrystalline titanium dioxide functional film is characterized by comprising the following steps: providing a substrate;
alternately depositing a titanium dioxide film layer and a grain growth inhibiting film layer on the substrate, wherein the grain growth inhibiting film layer is a metal oxide layer with an amorphous structure, and the thickness of the grain growth inhibiting film layer is 0.5-1.5 nm;
the deposition method comprises a chemical vapor deposition method, a magnetron sputtering method or an atomic layer deposition method.
8. The preparation method according to claim 7, wherein the method for preparing the nanocrystalline titanium dioxide functional film by adopting the atomic layer deposition method comprises the following steps:
(1) providing a substrate;
(2) designing the total thickness of the nanocrystalline titanium dioxide functional film, the thickness of each titanium dioxide film layer and the material and thickness of each crystal grain growth inhibition film layer according to requirements;
(3) determining the deposition temperature, the deposition rate of the titanium dioxide film layer, the deposition rate of the grain growth inhibition film layer, the sub-cycle times N of the titanium dioxide film layer, the sub-cycle times m of the grain growth inhibition film layer and the total cycle times N; and with H2O is used as an oxygen source, inert gas is used as carrier gas and purge gas, and an atomic layer deposition method is adopted for deposition;
(4) introducing a titanium source into the ALD vacuum chamber at the deposition temperature, wherein the cycle number is n, and obtaining a titanium dioxide film layer;
(5) introducing an aluminum source or a hafnium source into the ALD vacuum chamber at the deposition temperature, wherein the cycle number is m, and obtaining a crystal grain production inhibition layer;
(6) and (5) repeating the step (4) and the step (5) for N times, wherein the nanocrystalline titanium dioxide functional film has a grain growth inhibition film layer structure.
9. The method according to claim 8,
the titanium source is titanium tetrachloride;
the aluminum source is trimethyl aluminum;
the hafnium source is tetra (methylethylamine) hafnium or tetra (dimethylamine) hafnium.
10. The method according to claim 8,
the deposition temperature is 200-350 ℃, and the crystal structure of the obtained titanium dioxide thin film layer is anatase type.
CN202110484165.0A 2021-04-30 2021-04-30 Nanocrystalline titanium dioxide functional film and preparation method thereof Pending CN113235048A (en)

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CN101036200A (en) * 2004-08-13 2007-09-12 财团法人神奈川科学技术研究院 Transparent conductor, transparent electrode, solar cell, luminescent device and display panel
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