Semiconductor material precursors, metal targets, and methods of making and using

Abstract

The embodiment of the application provides a semiconductor material precursor, a metal target material and a preparation method and application, and relates to the field of semiconductor materials. The preparation method of the semiconductor material precursor comprises the following steps: mixing and stirring and grinding metal oxide powder and hydrogen peroxide, so as to oxidize metal ions in the metal oxide powder; the particle size of the metal oxide powder is 50-500 nm, and the concentration of the hydrogen peroxide is 20wt%-70wt%. After the hydrogen peroxide is mixed with the metal oxide as an oxidizing agent and is stirred and ground, the particles of the metal oxide can be uniformly dispersed, the hydrogen peroxide can be fully contacted with the metal oxide, the low-valence metal ions in the metal oxide can be well oxidized, and the phenomenon of low-valence cations in the metal oxide is greatly reduced; in addition, the hydrogen peroxide can be easily eliminated, and the purity of the semiconductor material precursor is not affected.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of semiconductor materials, in particular, to a semiconductor material precursor, a metal target material and a preparation method and application. BACKGROUND

[0002] In the field of semiconductor production equipment, metal compound raw materials are often used. For example, SnO2 can be used as a target material in semiconductor production equipment. As a component of the target material, SnO2 needs to maintain a positive four valence to ensure excellent photoelectric performance of the material.

[0003] Currently, due to the limitations of production methods, metal oxide powders such as SnO2 and TiO2 generated by methods such as solution method, sol method, hydrothermal method, chemical vapor deposition, and spray drying have a large number of lattice defects, especially low-valence cation lattice defects (low-valence cation refers to the separation of oxygen atoms or oxygen ions in the lattice of metal oxides or other oxygen-containing compounds, resulting in vacancies due to oxygen deficiency). Low-valence cations mean that there are a large number of low-valence metal ion phases (such as SnO phase and TiO phase) in metal oxide powders such as SnO2 and TiO2, which will affect the optical transmittance and electrical conductivity of the prepared oxide conductive thin film (see Li Quan et al. in the article "Thermal Treatment and Microstructure of Tin Dioxide Nanopowder"). The transmittance of the thin film decreases near 400 nm and 600 nm wavelengths, the carrier concentration of the thin film decreases, and the mobility decreases. SUMMARY

[0004] The present application provides a semiconductor material precursor, a metal target material and a preparation method and application. The lattice defects in the semiconductor material precursor prepared by the preparation method can be greatly reduced. When the metal target material prepared by the semiconductor material is used to deposit an oxide conductive thin film, the electrical conductivity and optical transmittance of the electronic device can be greatly improved.

[0005] In a first aspect, the present application provides a preparation method of a semiconductor material precursor, which includes the following steps: mixing and stirring a metal oxide powder with hydrogen peroxide and grinding to oxidize the metal ions in the metal oxide powder; the particle size of the metal oxide powder is 50-500 nm, and the concentration of the hydrogen peroxide is 20wt%-70wt%.

[0006] In the technical scheme, hydrogen peroxide is mixed with the metal oxide and then stirred and ground, which can not only uniformly disperse the particles of the metal oxide, but also ensure that the hydrogen peroxide can fully contact the metal oxide, so that the low-valence metal ions in the metal oxide can be well oxidized, and the low-valence metal ions in the metal oxide are greatly reduced. In addition, the hydrogen peroxide can be easily eliminated, and the purity of the semiconductor material precursor is not affected.

[0007] The particle size of the metal oxide powder is controlled to be 50-500 nm, and the concentration of the hydrogen peroxide is controlled to be 20-70 mass percent, so that the low-valence metal ions in the metal oxide powder can be better oxidized, and the low-valence metal ions in the metal oxide are greatly reduced.

[0008] In a possible implementation, the temperature during the stirring and grinding is 20-70℃, and the stirring and grinding time is 5-60 min.

[0009] In the technical scheme, if the temperature during the stirring and grinding is too low and the time is too short, the reaction is not conducive to proceed, if the temperature is too high and the time is too long, the decomposition of the hydrogen peroxide is accelerated, the reaction risk is increased, and the reaction efficiency is reduced. Controlling the temperature during the stirring and grinding and the stirring and grinding time in a proper range can make the powder reaction sufficient and increase the utilization efficiency of the raw materials.

[0010] In a possible implementation, the temperature during the stirring and grinding is 40-50℃, and the stirring and grinding time is 30-40 min.

[0011] In a possible implementation, the mass ratio of the hydrogen peroxide to the metal oxide is 5-50:50-95.

[0012] In the technical scheme, too much hydrogen peroxide will release a large amount of heat and gas, and will also affect the stirring and grinding mixing of the powder, and too little hydrogen peroxide will affect the optimization effect of the powder. Therefore, the mass ratio of the hydrogen peroxide to the metal oxide should be controlled in a proper range.

[0013] In a possible implementation, the concentration of the hydrogen peroxide is 30wt%-40wt%.

[0014] In a possible implementation, the metal elements in the metal oxide powder include at least one of Sn, Ti, Bi, Sb, Ni, Ta, Nb, Mo, and W.

[0015] The inventor finds that in the technical scheme, low-valence metal ion lattice defects are often generated in the high-valence oxides of the metal elements, and therefore the metal oxide powder formed by the metal elements needs to be treated to eliminate the lattice defects.

[0016] In a possible implementation, after the stirring and grinding, a drying process is further included, the drying temperature is 80-200 DEG C, and the drying time is 20-60 min.

[0017] In a second aspect, the embodiments of the present application provide a semiconductor material precursor prepared by the method for preparing a semiconductor material precursor.

[0018] In the above technical solution, the semiconductor material precursor prepared by the method has few lattice defects and can be used to prepare a high-performance conductive film or electronic device.

[0019] In a third aspect, the embodiments of the present application provide a metal target material, which comprises the semiconductor material precursor of the second aspect.

[0020] In the above technical solution, the metal target material prepared by the method has few low-valence cation defects on the surface and is more conducive to preparing a high-performance conductive film.

[0021] In a fourth aspect, the embodiments of the present application provide an application of the metal target material of the third aspect in preparing a conductive oxide film of a solar cell. BRIEF DESCRIPTION OF DRAWINGS

[0022] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments of the present application will be briefly introduced as follows. It should be understood that the following drawings only show some embodiments of the present application, and therefore should not be regarded as a limitation on the scope, and other related drawings can also be obtained by those skilled in the art without creative labor on the basis of the drawings.

[0023] Figure 1 XPS spectra of SnO2 powder of the embodiment 1 of the present application before and after treatment;

[0024] Figure 2 XPS spectra of TiO2 powder of the embodiment 2 of the present application before and after treatment;

[0025] Figure 3 XPS spectra of MoO3 powder of the embodiment 3 of the present application before and after treatment;

[0026] Figure 4 XPS spectra of Nb2O5 powder of the embodiment 4 of the present application before and after treatment;

[0027] Figure 5 Absorption spectrum of a TCO film prepared by using the SnO2 metal target material of the embodiment 5 of the present application;

[0028] Figure 6The absorption spectrum of the TCO thin film prepared using the SnO2 metal target of Comparative Example 1 of this application is shown. Detailed Implementation

[0029] The inventors discovered that existing metal oxides such as SnO2 and TiO2 all exhibit varying degrees of lattice defects, particularly severe low-valence cation defects. These metal oxides are frequently used in the semiconductor field to fabricate semiconductor films or semiconductor manufacturing equipment. These low-valence cation defects affect the electrical conductivity and optical transmittance of electronic devices. Even with current PVD methods for preparing semiconductor films in an O2 atmosphere, the technical problem of severe low-valence cation defects remains largely unresolved.

[0030] Based on this technical problem, the inventors discovered that oxidizing metal oxides before they are used to prepare conductive films, conductive pastes, or metal targets can significantly reduce the presence of low-valence cation defects. To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Unless otherwise specified, specific conditions in the embodiments are performed according to conventional conditions or conditions recommended by the manufacturer. Reagents or instruments used without specified manufacturers are all commercially available conventional products.

[0031] The semiconductor material precursors and their preparation methods according to embodiments of this application will be described in detail below.

[0032] The preparation steps of the semiconductor material precursor in this embodiment are shown in the following order:

[0033] S100 Clean the mixing and grinding container.

[0034] In this step, one or more of the following can be used as cleaning solvents: quartz sand, deionized water, acetone, ethanol, dilute hydrochloric acid, etc., to perform ultrasonic cleaning on the stirring and grinding container.

[0035] Specifically, in this embodiment, quartz sand can be used to clean the grinding container first to reduce the adhesion of some hard-to-remove dirt on the inner surface of the container, thus achieving a preliminary cleaning effect; then dilute hydrochloric acid can be used to clean it to remove metal oxides and metal ions inside the container; then deionized water can be used to clean it to remove residual dilute hydrochloric acid and other water-soluble ions; and finally, organic solvents such as acetone and ethanol can be used to remove organic matter in the solvent.

[0036] S200. Mix the metal oxide and hydrogen peroxide in a grinding container and stir and grind.

[0037] In this step, the metal oxide is mixed with hydrogen peroxide with oxidizing property and then stirred and ground. This can not only oxidize the low-valence metal ions in the metal oxide into high-valence metal ions, greatly reducing the phenomenon of low-valence metal ions in the metal oxide, but also make the metal oxide powder restore the ideal stoichiometric ratio. In addition, hydrogen peroxide can also play a dispersing role. However, too much hydrogen peroxide will release a large amount of heat and gas, and will also affect the stirring and grinding of the powder. Too little hydrogen peroxide will affect the optimization effect of the powder. Therefore, in order to ensure the oxidation effect, the mass ratio of hydrogen peroxide to metal oxide is generally 5-50:50-95. Of course, hydrogen peroxide can be added in batches if necessary. In addition, in order to ensure the oxidation effect, the concentration of hydrogen peroxide is generally 20%-70%, specifically, it can be 30%-60%, more specifically, it can be 40%-50%, for example, the concentration of hydrogen peroxide is 25%, 35%, 45%, 55% or 65%.

[0038] In this step, in order to ensure that the metal oxide can fully contact with hydrogen peroxide during grinding and stirring, the particle size of the metal oxide powder needs to be small enough to uniformly disperse the metal oxide particles and accelerate the reaction through high surface energy during grinding and stirring. Therefore, the particle size of the metal oxide powder is generally 50-500 nm, specifically, it can be 100-400 nm, more specifically, it can be 200-300 nm, for example, the particle size of the metal oxide powder is 150 nm, 250 nm, 350 nm or 450 nm. The metal elements in the metal oxide powder include at least one of Sn, Ti, Bi, Sb, Ni, Ta, Nb, Mo and W.

[0039] For example, in this step, the temperature during stirring and grinding is 20-70°C, specifically, it can be 30-60°C, more specifically, it can be 40-50°C, for example, the temperature during stirring and grinding is 25°C, 35°C, 45°C, 55°C or 65°C; the stirring and grinding time is 5-60 min, specifically, it can be 10-50 min, more specifically, it can be 20-40 min, for example, the stirring and grinding time is 15 min, 25 min, 35 min, 45 min or 55 min.

[0040] S300, after S200, drying treatment is performed.

[0041] After the step S200, some hydrogen peroxide remains, and some water is generated after the hydrogen peroxide oxidizes the metal compound powder. Therefore, drying treatment is needed to remove the remaining hydrogen peroxide and the generated water. The drying treatment is generally performed at a temperature of 80-200°C, specifically, it can be 100°C, 120°C, 160°C, 180°C or 190°C; and the drying treatment is generally performed for 20-60 minutes, specifically, it can be 30 minutes, 40 minutes or 50 minutes. Moreover, the drying treatment is generally performed in a drying air tank.

[0042] In addition, in order to better oxidize the metal oxide powder, a metal precursor with substantially no low-valence cation is prepared, and the steps S200-S300 can be repeated multiple times.

[0043] The semiconductor material precursor prepared by the above preparation method can be used to prepare a metal target, and an oxide conductive film can also be prepared using a metal target containing the semiconductor material precursor.

[0044] The features and performances of the present application are further described in detail below in combination with examples.

[0045] Example 1

[0046] The present example provides a SnO2-based semiconductor material precursor, and the preparation method thereof is specifically as follows:

[0047] S100, sequentially clean the stirring and grinding container with quartz sand, dilute hydrochloric acid, deionized water, acetone and ethanol.

[0048] S200, put 10 g of SnO2 powder with an average particle size of 50 nm and 2 ml of H2O2 solution with a mass fraction of 30% into the stirring and grinding container, mix and perform stirring and grinding, the stirring and grinding time is 1 hour, and the stirring and grinding temperature is 45°C.

[0049] S300, put the stirring and grinding container in S200 into a drying air tank to perform drying treatment, the drying temperature is 80°C, and the drying time is 1 hour.

[0050] S400, repeat S200-S300 three times to prepare a SnO2-based semiconductor material precursor.

[0051] Example 2

[0052] The present example provides a TiO2-based semiconductor material precursor, and the preparation method thereof is specifically as follows:

[0053] S100, sequentially clean the stirring and grinding container with quartz sand, dilute hydrochloric acid, deionized water, acetone and ethanol.

[0054] S200, 10 g of TiO2 powder with an average particle size of not more than 100 nm and 5 ml of 20% H2O2 solution by mass fraction are put into a stirring and grinding container to mix and perform stirring and grinding, the stirring and grinding time is 1 hour, and the stirring and grinding temperature is 45°C.

[0055] S300, the stirring and grinding container in S200 is put into a drying air box to perform drying treatment, the drying temperature is 100°C, and the drying time is 1 h.

[0056] S400, steps S200-S300 are repeated twice to prepare a TiO2-based semiconductor material precursor.

[0057] Example 3

[0058] The embodiment provides a MoO3-based semiconductor material precursor, and a preparation method thereof is as follows:

[0059] S100, a stirring and grinding container is sequentially cleaned by using quartz sand, dilute hydrochloric acid, deionized water, acetone and ethanol.

[0060] S200, 10 g of MoO3 powder with an average particle size of not more than 100 nm and 2 ml of 20% H2O2 solution by mass fraction are put into a stirring and grinding container to mix and perform stirring and grinding, the stirring and grinding time is 1 hour, and the stirring and grinding temperature is 45°C.

[0061] S300, the stirring and grinding container in S200 is put into a drying air box to perform drying treatment, the drying temperature is 80°C, and the drying time is 1 h.

[0062] S400, steps S200-S300 are repeated twice to prepare a MoO3-based semiconductor material precursor.

[0063] Example 4

[0064] The embodiment provides a Nb2O5-based semiconductor material precursor, and a preparation method thereof is as follows:

[0065] S100, a stirring and grinding container is sequentially cleaned by using quartz sand, dilute hydrochloric acid, deionized water, acetone and ethanol.

[0066] S200, 10 g of Nb2O5 powder with an average particle size of 500 nm and 3 ml of 40% H2O2 solution by mass fraction are put into a stirring and grinding container to mix and perform stirring and grinding, the stirring and grinding time is 1 hour, and the stirring and grinding temperature is 45°C.

[0067] S300, the stirring and grinding container in S200 is put into a drying air box to perform drying treatment, the drying temperature is 80°C, and the drying time is 1 h.

[0068] S400, repeat steps S200-S300 twice to obtain the Nb2O5-based semiconductor material precursor.

[0069] Example 5

[0070] The embodiment provides a SnO2 metal target, and a preparation method thereof is as follows:

[0071] S100, sequentially clean the stirring and grinding container by using quartz sand, dilute hydrochloric acid, deionized water, acetone and ethanol.

[0072] S200, put 40g SnO2 powder with an average particle size of not more than 100nm and 2ml H2O2 solution with a mass fraction of 30% into the stirring and grinding container, mix and perform stirring and grinding, the stirring and grinding time is 1 hour, and the stirring and grinding temperature is 45 DEG C.

[0073] S300, put the stirring and grinding container in S200 into a dry blast box to perform drying treatment, the drying temperature is 200 DEG C, the drying time is 20min, and the SnO2-based semiconductor material precursor is obtained.

[0074] S400, repeat steps S200-S300 three times to obtain the SnO2-based semiconductor material precursor.

[0075] S500, mix the SnO2-based semiconductor material precursor in S400 with 4.0g SnF2 powder, and perform the steps of ball milling, pre-sintering, ball milling, pre-sintering, drying, pressing and sintering to obtain the SnO2 metal target.

[0076] Comparative Example 1

[0077] The embodiment provides a SnO2 metal target, and a preparation method thereof is as follows:

[0078] Mix 40g SnO2 powder with an average particle size of not more than 100nm with 4.0g SnF2 powder, and perform the steps of ball milling, pre-sintering, ball milling, pre-sintering, drying, pressing and sintering to obtain the SnO2 metal target.

[0079] Application Example

[0080] XPS Spectrum Test

[0081] XPS (X-ray photoelectron spectroscopy) is used to test the metal oxide powder before and after treatment in Examples 1-4, and the XPS spectrum of each example is shown in Figures 1-4 .

[0082] Figure 1 The XPS spectra of SnO2 powder before and after treatment are shown respectively, andFigure 1 It can be seen that the SnO2 powder before treatment has defects of low valence cations (there is a peak at the position of 529.15 eV), and the SnO2 powder after treatment has no defects of low valence cations, and the content ratio of Sn and O elements in the SnO2 powder is measured by the spectrum area, and the results are shown in Table 1.

[0083] Table 1 Element content ratio of SnO2 powder before and after treatment in Example 1 measured by XPS

[0084]

[0085] It can be seen from Table 1 that the oxygen content of the SnO2-based semiconductor material precursor in Example 1 is greatly increased, and the stoichiometric ratio of Sn and O is closer to the ideal value 1:2. Among them, Sn3d represents testing the electrons in the 3d orbit of Sn, thereby obtaining the content of Sn; O1s represents testing the electrons in the 1s orbit of O, thereby obtaining the content of O.

[0086] Figure 2 XPS spectra of TiO2 powder before and after treatment are shown respectively, wherein (a) is the XPS spectrum of Ti before and after treatment, and (b) is the XPS spectrum of O before and after treatment. The content ratio of Ti and O elements in the TiO2 powder before and after treatment is measured by the spectrum area, and the results are shown in Table 2.

[0087] Table 2 Element content ratio of TiO2 powder before and after treatment in Example 2 measured by XPS

[0088]

[0089]

[0090] It can be seen from Table 2 that the oxygen content of the TiO2-based semiconductor material precursor in Example 2 is greatly increased, and the stoichiometric ratio of Ti and O is closer to the ideal value 1:2. Among them, Ti2p represents testing the electrons in the 2p orbit of Ti, thereby obtaining the content of Ti.

[0091] Figure 3 XPS spectra of MoO3 powder before and after treatment are shown respectively, wherein (a) is the XPS spectrum of Mo before and after treatment, and (b) is the XPS spectrum of O before and after treatment. Figure 3 From the XPS peak position results in Table 3, it can be seen that the electron binding energy of Mo3d increases, indicating that the bonding energy of Mo and O increases, and the oxygen content of the semiconductor material precursor increases.

[0092] The content ratio of Mo and O elements in the MoO3 powder before and after treatment is measured by the spectrum area, and the results are shown in Table 3.

[0093] Table 3 Element content ratio of MoO3 powder before and after treatment in Example 3 measured by XPS

[0094]

[0095] As shown in Table 3, the oxygen content of the MoO3-based semiconductor material precursor in Example 3 is greatly increased, and the stoichiometric ratio of Mo to O is closer to the ideal value 1:3. Mo3d represents testing the electrons in the 3d orbit of Mo, thereby obtaining the content of Mo.

[0096] Figure 4 XPS spectra of Nb2O5 powder before and after treatment are shown in Figures 2(a) and 2(b), respectively. Figure 2(a) is the XPS spectrum of Nb before and after treatment, and Figure 2(b) is the XPS spectrum of O before and after treatment. Figure 4 As shown in the XPS peak position results in Figure 2, the binding energy of Nb3d electrons increases, indicating that the bonding energy between Nb and O increases, and the oxygen content of the semiconductor material precursor increases.

[0097] The content of Mo and O elements before and after treatment of the Nb2O5 powder is measured by the spectrum area, and the results are shown in Table 4.

[0098] Table 4 Element content ratio of Nb2O5 powder before and after treatment in Example 4 measured by XPS

[0099]

[0100] As shown in Table 4, the oxygen content of the Nb2O5-based semiconductor material precursor in Example 4 is greatly increased, and the stoichiometric ratio of Nb to O is closer to the ideal value 2:5. As shown in the XPS peak position results in Figure 2, the binding energy of Nb3d electrons increases, indicating that the bonding energy between Nb and O increases, and the oxygen content of the semiconductor material precursor also increases. Nb3d represents testing the electrons in the 3d orbit of Mo, thereby obtaining the content of Nb. Figure 4

[0101] Therefore, the semiconductor material precursor in this embodiment has fewer lattice defects, and the conductivity and optical transmittance of the conductive film prepared using the semiconductor material precursor in this embodiment are also improved, which greatly improves the efficiency of electronic devices when used to prepare electronic devices.

[0102] Metal target performance test

[0103] The SnO2 metal target in Example 5 and Comparative Example 1 was plated by a radio frequency magnetron sputtering device, and the plating conditions were as follows: glass substrate, 30 W, 0.4 Pa, 27 min, and 200°C.

[0104] ​The absorption spectrum of the plated TCO (transparent conductive oxide) film was tested by using a UV-visible spectrophotometer, and the spectrum is shown in Figures 5-6 .

[0105] As can be seen from Figure 5 and Figure 6 , compared with the TCO film prepared by using the metal target of Comparative Example 1, the TCO film prepared by using the metal target of Example 5 has an increased light transmittance in the range of 400-600 nm.

[0106] The TCO films were respectively subjected to electrical testing by using a Hall effect tester, and the test results are shown in Table 5.

[0107] Table 5 Carrier concentration, carrier mobility, resistivity and film thickness of TCO film

[0108]

[0109]

[0110] As can be seen from Table 5, the TCO film prepared by using the SnO2 metal target of Example 5 has a greatly improved carrier concentration and carrier mobility.

[0111] The above only describes the embodiments of the present application and is not used to limit the protection scope of the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method of producing a semiconductor material precursor, characterized by, It comprises the following steps: Mixing and stirring grinding the metal oxide powder with hydrogen peroxide to oxidize the metal ions in the metal oxide powder; the particle size of the metal oxide powder is 50-500 nm, the concentration of the hydrogen peroxide is 20wt%-70wt%, the temperature during stirring grinding is 20-70℃, and the stirring grinding time is 5-60 min; The metal elements in the metal oxide powder include at least one of Sn, Ti, Bi, Sb, Ni, Ta, Nb, Mo, W, and the mass ratio of the hydrogen peroxide to the metal oxide is 5-50:50-95.

2. The method of claim 1, wherein the semiconductor material precursor is prepared by a method comprising: The temperature during stirring grinding is 40-50℃, and the stirring grinding time is 30-40 min. ​ 3. The method of claim 1, wherein the semiconductor material precursor is prepared by a process comprising: The concentration of the hydrogen peroxide is 30wt%-40wt%. ​ 4. The method of claim 1, wherein the semiconductor material precursor is prepared by a method comprising: After stirring grinding, a drying treatment step is further included, the drying temperature is 80-200℃, and the drying time is 20-60 min. ​

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