CN110777366B - Nanocrystalline silicon oxide film and photoresist-like silicon oxide material prepared from same - Google Patents

Nanocrystalline silicon oxide film and photoresist-like silicon oxide material prepared from same Download PDF

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CN110777366B
CN110777366B CN201910977268.3A CN201910977268A CN110777366B CN 110777366 B CN110777366 B CN 110777366B CN 201910977268 A CN201910977268 A CN 201910977268A CN 110777366 B CN110777366 B CN 110777366B
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silicon oxide
photoresist
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nanocrystalline
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CN110777366A (en
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陈王华
郑珍
张晓伟
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Ningbo University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C23C16/402—Silicon dioxide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/52—Controlling or regulating the coating process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • 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
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Abstract

The invention belongs to the technical field of microelectronics and solar cells, and relates to a photoresist-like silicon oxide material and a preparation method thereof. The photoresist-like silicon oxide material comprises a substrate and a nanocrystalline silicon oxide film nc-SiOxThe nanocrystalline silicon oxide film is of a double-layer structure and comprises a first layer film with high solubility and low absorptivity and a second layer film with high absorptivity and low solubility, wherein the refractive index n1 of the first layer film is greater than that of the second layer film. The preparation method of the photoresist-like silicon oxide material comprises the steps of preparing a substrate, depositing a silicon oxide double-layer film, performing ultraviolet laser ablation, and removing nc-SiOx. The double-layer nanocrystalline silicon oxide film of the invention realizes that the absorptivity of the photoresist film is increased on the premise of not reducing the solubility, and simultaneously adopts a radio frequency plasma enhanced chemical vapor deposition mode to coat the film, thereby overcoming the defect that the photoresist is incompatible with high temperature and plasma exposure, and greatly simplifying the preparation process.

Description

Nanocrystalline silicon oxide film and photoresist-like silicon oxide material prepared from same
Technical Field
The invention belongs to the technical field of microelectronics and solar cells, relates to a novel dielectric structure and a preparation process thereof, and particularly relates to a nanocrystalline silicon oxide film and a photoresist-like silicon oxide material prepared from the nanocrystalline silicon oxide film.
Background
The photolithography technique is a process of transferring image information designed on a mask to a wafer or a dielectric layer through processes of exposure, development, etching and the like by using a photoresist (i.e., a photoresist) as an intermediate medium under the action of light. Photolithography, which is an important process in the production of planar transistors and integrated circuits, allows good control of patterning by exposure, and is now widely used in the crystalline silicon industry, for example in the field of semiconductor-based materials such as microelectronics and solar cells.
Photoresists are photosensitive materials in the process of pattern replication, are wide in variety and complex in preparation technology. The conventional silicon wafer lithography technology comprises 8 steps, which are sequentially as follows: 1) cleaning a silicon wafer; 2) plating photoresist; 3) Pre-baking; 4) calibrating and template exposure; 5) postbaking; 6) dissolving the exposed photoresist; 7) plating a silicon dioxide hard mask; 8) and removing the residual photoresist. However, this process is prone to cause adhesion of the photoresist to the underlying layer of crystalline silicon. The adhesiveness represents the strength of the photoresist adhered to the substrate, and the high adhesiveness easily increases the demolding difficulty and damages the microstructure; and the adhesive property is small and the degumming is easy to cause. Although local PN-junction local metal contacts can also be deposited through a physical shadow mask, this method will diffuse under the mask after deposition and the diffusion area is difficult to determine since there is always a space between the mask and the substrate.
The film-forming property, hardness and viscosity, curing speed, etching resistance and the like of the photoresist are all factors to be considered for evaluating the performance of the photoresist. The main function of the photoresist is to perform micro pattern transfer as a resist, and thus better etching selectivity and etching resistance are required. Thermosetting and photosensitive photoresists have faster curing speeds, while thermoplastic photoresists have better cleaning properties than thermosetting photoresists but have poorer thermal stability. Since the photoresist is a polymer, it is incompatible with high temperatures (>150 ℃) and plasma exposure. In order to prepare an efficient IBC cell, a doped double-layer hydrogenated silicon film, which is highly crystallized or partially amorphous and has a local crystallinity close to that of the underlying film, is deposited at a low temperature on the wafer surface by a Plasma Enhanced Chemical Vapor Deposition (PECVD) method in the literature (equivalent. simple processing of back-contacted silicon heterojunction solar cells, 2:17072), so that a double-layer film having specific heterojunction electrical properties can be formed, and mask alignment and preparation processes are simplified. Plasma chemical vapor deposition is a common method for forming thin films on substrates, but the introduction of photoresist in PECVD can contaminate the deposition process.
In summary, the existing photolithography technique has certain limitations. Therefore, the manufacture of a photolithographic material that is both resistant to heat and plasma, and the realization of a compromise between the two conflicting parameters of light absorption and dissolution rate, is a problem that needs to be solved in the present day for improving semiconductor manufacturing and photolithography techniques.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nanocrystalline silicon oxide film, a photoresist-like silicon oxide material and a preparation method thereof, develops a new dielectric structure, and can be used in the photoetching technical fields of crystalline silicon texturing, cross back contact solar cells and the like.
The above object of the present invention is achieved by the following technical solutions:
a nanocrystalline silicon oxide film is prepared from hydrogenated amorphous silicon oxide (a-SiO)xH) a multilayer film formed by embedding silicon nanocrystals in a matrix, the multilayer film including at least an L1 layer and an L2 layer, the L1 layer and the L2 layer having different refractive indices.
Preferably, the refractive index (n1) of the L1 layer in the above multilayer film of the present invention is 1.5 to 4 at 600nm, and the refractive index (n2) of the second layer film is 1.2 to 2.5 at 600 nm.
Preferably, the thickness of the L1 layer in the multilayer film of the present invention is 20 to 60nm, and the thickness of the L2 layer is 30 to 100 nm.
Nanocrystalline silicon oxide (nc-SiO)x) The film material has the characteristics of high conductivity, photoluminescence and the like, and the band gap is adjusted by changing the grain size and the crystallization rate, so that the film material can be applied to absorption of light of different wave bands by optoelectronic devices. The nanocrystalline silicon oxide film of the invention has the advantages that the grain diameter of the nanocrystals contained in the L1 layer is larger, the grain diameter of the nanocrystals in the L2 layer is smaller, and the volume fraction of the silicon nanocrystals contained in the L1 layer is larger than that of the silicon nanocrystals in the L2 layer, so that the crystallization ratio of the silicon nanocrystals and the refractive indexes of the L1 layer and the L2 layer are adjusted, and the n1 layer is made to have larger grain diameter than that of the nanocrystals contained in the L2 layer>n2。
The invention also aims to provide a photoresist-like silicon oxide material which comprises a substrate and the multilayer nanocrystalline silicon oxide film.
Preferably, the substrate material used in the present invention includes, but is not limited to, silicon dioxide, silicon carbide, silicate glass, silicon nitride, germanium nitride, or SOI.
Further preferably, in the present invention, the substrate is bare crystalline silicon.
Nanocrystalline silicon oxide (nc-SiO) in the present inventionx) The multilayer film comprises a high solubility, low absorption (high index of refraction) L1 layer and a high absorption (low index of refraction), low solubility L2 layer. The invention combines the L1 layer with high refractive index and the L2 layer with low refractive index, and realizes that the light absorption rate of the photoresist film is increased on the premise of not reducing the solubility.
In another aspect, the present invention further provides a method for manufacturing the photoresist-like silicon oxide material, including the following steps:
preparing a substrate;
depositing a multi-layer nanocrystalline silicon oxide film comprising an L1 layer and an L2 layer on the substrate;
and carrying out mask alignment according to the required pattern, and then carrying out laser exposure to obtain the photoresist-like silicon oxide material.
The photoresist needs to satisfy both strong absorption at a specific wavelength and easy removal by post-treatment, i.e., high light absorption and high dissolution rate. In the existing photoresist material, the two parameters are mutually contradictory, and the material with strong light absorption has weak solubility in the solution and is difficult to remove, so the two parameters can not be satisfied at the same time. According to the invention, the silicon nanocrystals are used as a high-absorptivity material in ultraviolet-visible light to be combined with an amorphous silicon oxide substrate, and the silicon oxide multilayer film containing the silicon nanocrystals is obtained through plasma enhanced chemical vapor deposition. The multilayer film of the present invention can prepare a photoresist material having high solubility and high absorptivity by changing the crystallization ratio of nanocrystals and the oxygen content such that the refractive index of the L1 layer is greater than that of the L2 layer.
Preferably, the deposition method of the present invention is a radio frequency plasma enhanced chemical vapor deposition method (RF-PECVD); the deposition conditions of the L1 layer were: temperature: 100-: 2.0Torr, Power Density: 90-160mW/cm2，SiH4：10-12SCCM，H2：200-250SCCM，CO2: 5 SCCM; the deposition conditions of the L2 layer were: temperature: 100-: 2.0Torr, Power Density: 100-180mW/cm2，SiH4：10-12SCCM，H2：150-220SCCM，CO2： 15SCCM。
The plasma enhanced chemical vapor deposition method is one of the most effective methods for depositing the nanocrystalline silicon oxide film, but different process parameters have great influence on the structure, the crystallization state, the photoelectric characteristics and the like of the nanocrystalline silicon film. Within a certain range, the deposition rate of the film is increased along with the increase of the deposition temperature, and the increase of the deposition temperature can promote the growth of crystal nuclei, further increase the orderliness of the film, and is beneficial to the increase of the light dark conductivity and the deposition speed, but the photosensitivity is slightly reduced. The hydrogen plasma environment is beneficial to the conversion of the film from amorphous to crystalline, and the increase of the hydrogen dilution ratio can improve the crystallization rate, the grain size and the light-dark conductivity of the film, but can reduce the deposition rate. Increasing the rf power can increase the crystallization rate, grain size, and deposition rate of the film, while too high rf power can lead to a decrease in the conductivity and photosensitivity of the film. Therefore, the obtained nc-SiO needs to be obtained by adjusting the parameters of the deposition processxThe nanocrystalline silicon in the thin film has proper crystallization ratio and grain size, so that the refractive indexes of the L1 layer and the L2 layer are adjusted to meet the requirement.
The multilayer nanocrystalline silicon oxide film has good process compatibility, so the prepared photoresist-like silicon oxide material can be widely applied to the technical field of microelectronics, such as crystalline silicon texturing, preparation of cross back contact solar cells and the like.
The invention also provides a semiconductor device which is prepared by removing the multilayer nanocrystalline silicon oxide film in the unexposed area by fluoride through one or more steps of ion implantation, high-temperature diffusion or metallization of the photoresist-like silicon oxide material.
The fluoride according to the invention is preferably hydrofluoric acid or silicon tetrafluoride plasma.
Further, the preparation method of the semiconductor device comprises the following steps:
preparing a substrate;
depositing an L1 layer on the substrate, and then depositing an L2 layer on the L1 layer to form a double-layer nanocrystalline silicon oxide film;
carrying out mask alignment according to the required pattern, and then carrying out laser exposure to obtain a photoresist-like silicon oxide material;
performing one or more of ion implantation, high temperature diffusion, or metallization;
and removing the double-layer nanocrystalline silicon oxide film in the unexposed area by using fluoride to obtain the semiconductor device.
Further, when deposition of a PN junction is involved, the method for manufacturing a semiconductor device includes the steps of:
preparing a substrate;
when the PN junction is prepared, firstly depositing an L2 layer on the substrate as a protective layer, and then depositing an L1 layer on the L2 layer to form a double-layer nanocrystalline silicon oxide film;
carrying out mask alignment according to the required pattern, and then carrying out laser exposure to obtain a photoresist-like silicon oxide material;
and removing the nanocrystalline silicon oxide film in the unexposed area by using fluoride.
The deposition sequence of the L1 layer and the L2 layer can be switched according to the requirements of different application structures. In the case where ion implantation, metallization and high temperature diffusion are required, the L1 layer is deposited first, and no post-laser ablation treatment is required before further implantation, metallization or diffusion. And the deposition of PN junction requires a defect-free substrate surface, a protective layer is formed by depositing an L2 layer with the thickness of a few nanometers before depositing an L1 layer, so that the damage of laser ablation on the substrate surface is prevented. After laser ablation, with 5% hydrofluoric acid (HF) solution or silicon tetrafluoride (SiF)4) Plasma can remove protective layer and nc-SiO fastxA film.
Compared with the prior art, the invention has the following advantages:
1. the invention develops a novel dielectric structure, and double-layer films with different refractive indexes are prepared by embedding silicon nanocrystals in a hydrogenated amorphous silicon oxide matrix, and comprise an L1 layer with high solubility and low absorptivity and an L2 layer with high absorptivity and low solubility, so that the requirement of strong absorption at a specific wavelength is met, and the films can be easily removed through post-treatment.
2. The method for manufacturing the photoresist-like silicon oxide adopts the radio frequency plasma enhanced chemical vapor deposition mode to coat the film, greatly reduces the deposition temperature, overcomes the defect that the photoresist is incompatible with high temperature and plasma exposure, and simplifies the preparation process.
Drawings
FIG. 1 is a double layer nanocrystalline silicon oxide film of example 1.
Fig. 2 is a double-layer nanocrystalline silicon oxide film of example 2.
FIG. 3 is a schematic illustration of the deposition of a bilayer nanocrystalline silicon oxide film in example 3.
FIG. 4 is an absorption spectrum of a nano-crystalline silicon oxide double-layer thin film in example 3.
FIG. 5 is a graph comparing the removal of the nano-crystalline silicon oxide bilayer film of example 9 by a 5% hydrogen fluoride solution before and after the removal.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described and illustrated with reference to the drawings, but the present invention is not limited to these embodiments. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
Example 1
As shown in fig. 1, a nanocrystalline silicon oxide film is a multilayer film formed by embedding silicon nanocrystals in a hydrogenated amorphous silicon oxide matrix, and the multilayer film sequentially comprises an L1 layer and an L2 layer from bottom to top, wherein the refractive index of the L1 layer is 2.3 at 600nm, and the refractive index of the L2 layer is 1.6 at 600 nm; the thickness of the L1 layer is 50nm, and the thickness of the L2 layer is 90 nm; wherein the volume fraction of the silicon nanocrystals in the L1 layer is greater than the volume fraction of the silicon nanocrystals in the L2 layer.
Example 2
As shown in fig. 2, a nanocrystalline silicon oxide film is a multilayer film formed by embedding silicon nanocrystals in a hydrogenated amorphous silicon oxide matrix, and the multilayer film sequentially comprises an L2 layer and an L1 layer from bottom to top, wherein the refractive index of the L1 layer is 2.9 at 600nm, and the refractive index of the L2 layer is 1.8 at 600 nm; the thickness of the L1 layer is 60nm, and the thickness of the L2 layer is 80 nm; wherein the volume fraction of the silicon nanocrystals in the L1 layer is greater than the volume fraction of the silicon nanocrystals in the L2 layer.
Example 3
As shown in fig. 3, a method for preparing a photoresist-like silicon oxide includes the following steps:
preparing a glass substrate (Corning 1737) as shown in fig. 3 (a);
first deposit L1 layer on the substrate, deposition temperature: 150 ℃, pressure: 2.0Torr, Power Density: 100mW/cm2，SiH4：12SCCM，H2：200SCCM，CO2: 5SCCM with a thickness of 50 nm; then an L2 layer was deposited on the L1 layer at a temperature: 150 ℃, pressure: 2.0Torr, Power Density: 100mW/cm2， SiH4：12SCCM，H2：200SCCM，CO2: 15SCCM with a thickness of 90 nm; as shown in fig. 3 (b), in which the refractive index n1 of the L1 layer is 2.3(600nm), and the refractive index n2 of the L2 layer is 1.6(600 nm);
ultraviolet laser ablation: mask alignment is performed according to the required pattern, and then laser exposure is performed to obtain a photoresist-like silicon oxide material, as shown in fig. 3 (c).
The absorbance of the above-mentioned nanocrystalline silica bilayer film was measured by an ultraviolet-visible spectrophotometer, and it can be seen from FIG. 4 that it has a maximum absorption at a wavelength of 355 nm. Note that nc-SiO of this examplexThe bilayer film is deposited on glass for measurement, so that the actual nc-SiOxThe absorbance of the double-layer film is subtracted from the absorbance of the glass substrate by the measured value.
Example 4
The preparation method of the photoresist-like silicon oxide comprises the following steps:
preparing a bare crystal silicon substrate without a natural oxide;
first deposit L1 layer on the substrate, deposition temperature: 160 ℃ and pressureForce: 2.0Torr, Power Density: 100mW/cm2，SiH4：12SCCM，H2：200SCCM，CO2: 5SCCM with a thickness of 50 nm; then an L2 layer was deposited on the L1 layer at a temperature: 140 ℃, pressure: 2.0Torr, Power Density: 120mW/cm2， SiH4：12SCCM，H2：180SCCM，CO2: 15SCCM with a thickness of 90 nm; wherein the refractive index n1 of the L1 layer is 2.2(600nm), the refractive index n2 of the L2 layer is 1.7(600 nm);
ultraviolet laser ablation: and carrying out mask alignment according to the required pattern, and then carrying out laser exposure to obtain the photoresist-like silicon oxide material.
Example 5
The preparation method of the photoresist-like silicon oxide comprises the following steps:
preparing a bare crystal silicon substrate without a natural oxide;
first deposit L1 layer on the substrate, deposition temperature: 180 ℃, pressure: 2.0Torr, Power Density: 120mW/cm2，SiH4：12SCCM，H2：200SCCM，CO2: 5SCCM with a thickness of 20 nm; then an L2 layer was deposited on the L1 layer at a temperature: 120 ℃, pressure: 2.0Torr, Power Density: 150mW/cm2， SiH4：12SCCM，H2：200SCCM，CO2: 15SCCM with a thickness of 95 nm; wherein the refractive index n1 of the L1 layer is 2.3(600nm), the refractive index n2 of the L2 layer is 1.5(600 nm);
ultraviolet laser ablation: and carrying out mask alignment according to the required pattern, and then carrying out laser exposure to obtain the photoresist-like silicon oxide material.
Example 6
The preparation method of the photoresist-like silicon oxide comprises the following steps:
preparing a bare crystal silicon substrate without a natural oxide;
first deposit L1 layer on the substrate, deposition temperature: 180 ℃, pressure: 2.0Torr, Power Density: 120mW/cm2，SiH4：12SCCM，H2：240SCCM，CO2: 5SCCM with a thickness of 50 nm; then an L2 layer was deposited on the L1 layer at a temperature: 150 ℃, pressure: 2.0Torr, Power Density: 160mW/cm2， SiH4：12SCCM，H2：200SCCM，CO2: 15SCCM with a thickness of 70 nm; wherein the refractive index n1 of the L1 layer is 3.7(600nm), the refractive index n2 of the L2 layer is 2.3(600 nm);
ultraviolet laser ablation: and carrying out mask alignment according to the required pattern, and then carrying out laser exposure to obtain the photoresist-like silicon oxide material.
Example 7
The preparation method of the photoresist-like silicon oxide comprises the following steps:
preparing an n-type monocrystalline silicon substrate without a natural oxide;
first deposit an L2 layer on the substrate, temperature: 100 ℃, pressure: 2.0Torr, Power Density: 150mW/cm2，SiH4：12SCCM，B2H6：2SCCM，H2：150SCCM，CO2: 15SCCM with a thickness of 30 nm; depositing an L1 layer, wherein the deposition temperature is as follows: 150 ℃, pressure: 2.0Torr, Power Density: 100mW/cm2，SiH4：12SCCM，PH3：1SCCM，H2：200SCCM，CO2: 5SCCM with a thickness of 50 nm; wherein the refractive index n1 of the L1 layer is 2.3(600nm), the refractive index n2 of the L2 layer is 1.6(600 nm);
and carrying out mask alignment according to the required pattern, and then carrying out laser exposure to obtain the photoresist-like silicon oxide material.
Example 8
The preparation method of the photoresist-like silicon oxide comprises the following steps:
preparing a p-type monocrystalline silicon substrate without a natural oxide;
first deposit an L2 layer on the substrate, temperature: 100 ℃, pressure: 2.0Torr, Power Density: 150mW/cm2，SiH4：12SCCM，PH3：2SCCM，H2：150SCCM，CO2: 15SCCM with a thickness of 30 nm; depositing an L1 layer, wherein the deposition temperature is as follows: 150 ℃, pressure: 2.0Torr, Power Density: 100mW/cm2，SiH4：12SCCM，B2H6：1SCCM，H2：200SCCM，CO2: 5SCCM with a thickness of 50 nm; wherein the refractive index n1 of the L1 layer is 2.2(600nm),the refractive index n2 of the L2 layer was 1.5(600 nm);
and carrying out mask alignment according to the required pattern, and then carrying out laser exposure to obtain the photoresist-like silicon oxide material.
Example 9
A semiconductor device, its preparation method includes the following steps:
the photoresist-like silicon oxide material prepared in example 3 was further subjected to high-temperature diffusion, and a solid-state diffusion source was used, and a boron microcrystalline glass sheet and a porous ceramic body containing phosphorus pentoxide were used as p-type and n-type doped impurity sources, respectively. The temperature of boron doping diffusion is 950 ℃, and the diffusion time is 30 min; the temperature of phosphorus doping diffusion is 900 ℃, and the diffusion time is 30 min.
Finally, the double-layer nanocrystalline silicon oxide film of the unexposed area can be removed within 1 minute by using a 5% hydrofluoric acid solution, as shown in fig. 5, and the coplanar PN junction semiconductor device is prepared.
Example 10
A semiconductor device, its preparation method includes the following steps:
the photoresist-like silicon oxide material prepared in example 3 was further subjected to high-temperature diffusion, and a solid-state diffusion source was used, and a boron microcrystalline glass sheet and a porous ceramic body containing phosphorus pentoxide were used as p-type and n-type doped impurity sources, respectively. The temperature of boron doping diffusion is 850 ℃, and the diffusion time is 50 min; the temperature of phosphorus doping diffusion is 800 ℃, and the diffusion time is 50 min.
And finally, removing the double-layer nanocrystalline silicon oxide film of the unexposed area within 1 minute by using a 5% hydrofluoric acid solution to obtain the coplanar PN junction semiconductor device.
Example 11
A semiconductor device, its preparation method includes the following steps:
the photoresist-like silicon oxide material prepared in example 3 was further subjected to high-temperature diffusion, and a solid-state diffusion source was used, and a boron microcrystalline glass sheet and a porous ceramic body containing phosphorus pentoxide were used as p-type and n-type doped impurity sources, respectively. The temperature of boron doping diffusion is 850 ℃, and the diffusion time is 30 min; the temperature of phosphorus doping diffusion is 950 ℃, and the diffusion time is 20 min.
And finally, removing the double-layer nanocrystalline silicon oxide film of the unexposed area within 1 minute by using a 5% hydrofluoric acid solution to obtain the coplanar PN junction semiconductor device.
Example 12
A semiconductor device, its preparation method includes the following steps:
the photoresist-like silicon oxide material prepared in example 3 was further subjected to high-temperature diffusion, and a solid-state diffusion source was used, and a boron microcrystalline glass sheet and a porous ceramic body containing phosphorus pentoxide were used as p-type and n-type doped impurity sources, respectively. The temperature of boron doping diffusion is 950 ℃, and the diffusion time is 30 min; the temperature of phosphorus doping diffusion is 900 ℃, and the diffusion time is 30 min. And carrying out metallization after the PN junction is prepared, and heating and evaporating a coating film by adopting an electron beam to ensure that the metal aluminum film is uniformly distributed on the surface of the photoresist-like silicon oxide material.
And finally, removing the double-layer nanocrystalline silicon oxide film of the unexposed area by using a 5% hydrofluoric acid solution within 30 seconds to obtain the required semiconductor device.
Example 13
A semiconductor device, its preparation method includes the following steps:
ion implantation (boron doping) was performed on the photoresist-like silicon oxide material prepared in example 3; the nanocrystalline silicon oxide double-layer film of the unexposed area can be removed within 30 seconds by using a 5% hydrofluoric acid solution, and the coplanar PN junction semiconductor device is obtained.
Examples 14 to 18
Semiconductor devices were respectively prepared from the photoresist-like silicon oxide material prepared in example 4 by the preparation methods as in examples 9 to 13.
The film deposition sequence of examples 3-6 was deposition of L1 followed by L2, laser ablation followed by high temperature diffusion, ion implantation or metallization, and finally removal of the nanocrystalline silicon oxide film. In examples 7 to 8, boron and phosphorus were doped during the plasma cvd process to form PN junctions, and in order to protect the substrate surface from damage, an L2 layer was formed as a protective layer before the L1 layer was deposited, and the laser deposition was performedAfter ablation, the protective layer and nc-SiO can be quickly removed by using 5% hydrofluoric acid solutionxA film. The photoresist-like silicon oxide prepared by the embodiment of the invention has strong absorption at 355nm wavelength, and the film can be easily removed by post-treatment, and simultaneously, the requirements of high absorption rate and high dissolution rate are met. In addition, the conventional photoresist material is polymer and incompatible with high temperature and plasma exposure, so that the invention adopts a radio frequency plasma enhanced chemical vapor deposition method to deposit at the temperature of not more than 200 ℃, and the nano-crystal size of the L1 layer is larger than that of the L2 layer by adjusting the radio frequency power and the hydrogen dilution ratio to adjust the crystallization rate and the grain size of the film, thereby obtaining nc-SiO with different refractive indexesxA film.
The specific embodiments described herein are merely illustrative of the spirit of the invention and do not limit the scope of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (7)

1. The nanocrystalline silicon oxide film is characterized in that the nanocrystalline silicon oxide film is a double-layer film formed by embedding silicon nanocrystals in a hydrogenated amorphous silicon oxide substrate, the double-layer film comprises an L1 layer and an L2 layer, and the refractive indexes of the L1 layer and the L2 layer are different; the refractive index of the L1 layer in the double-layer film is 1.5-4 at 600nm, and the refractive index of the L2 layer is 1.2-2.5 at 600 nm; the thickness of the L1 layer in the double-layer film is 20-60nm, and the thickness of the L2 layer is 30-100 nm; the volume fraction of the silicon nanocrystals in the L1 layer is greater than the volume fraction of the silicon nanocrystals in the L2 layer.
2. A photoresist-like silicon oxide material comprising a substrate and a nanocrystalline silicon oxide film as claimed in claim 1.
3. A method of fabricating the photoresist-like silicon oxide material of claim 2, comprising the steps of:
preparing a substrate;
depositing a bilayer nanocrystalline silicon oxide film comprising a layer of L1 and a layer of L2 on the substrate;
and carrying out mask alignment according to the required pattern, and then carrying out laser exposure to obtain the photoresist-like silicon oxide material.
4. The method of claim 3, wherein the deposition process is RF plasma enhanced chemical vapor deposition; the deposition conditions of the L1 layer were: temperature: 100-: 2.0Torr, Power Density: 90-160mW/cm2，SiH4：10-12 SCCM，H2：200-250 SCCM，CO2 ：5 SCCM。
5. The method as claimed in claim 3 or 4, wherein the deposition conditions of the L2 layer are as follows: temperature: 100-: 2.0Torr, Power Density: 100-180mW/cm2，SiH4：10-12 SCCM，H2：150-220 SCCM，CO2 ：15 SCCM。
6. A semiconductor device made from the photoresist-like silicon oxide material of claim 2 by one or more of ion implantation, high temperature diffusion or metallization, and removing the unexposed areas of the multilayer nanocrystalline silicon oxide film with fluoride.
7. The semiconductor device according to claim 6, wherein the fluoride is hydrofluoric acid or silicon tetrafluoride plasma.
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