CN115572167A

CN115572167A - IWZO target material and preparation method and application thereof

Info

Publication number: CN115572167A
Application number: CN202211272544.4A
Authority: CN
Inventors: 陈明飞; 王金科; 刘永成; 郭梓旋; 徐胜利; 陈明高; 江长久; 王志杰; 莫国仁; 李跃辉
Original assignee: Enam Optoelectronic Material Co ltd
Current assignee: Enam Optoelectronic Material Co ltd
Priority date: 2022-10-18
Filing date: 2022-10-18
Publication date: 2023-01-06

Abstract

The invention discloses an IWZO target material and a preparation method and application thereof. The IWZO target material comprises In, W, zn and O, wherein In: w: zn =1: n: n × M; wherein N is more than or equal to 0.02 and less than 0.0721; m is more than or equal to 0.8 and less than 1.2. The IWZO target material prepared by adopting the atomic ratio has high density and good color uniformity, and does not generate nodulation and point discharge in the continuous use process. In addition, the oxide film prepared by adopting the IWZO target has low resistivity, low surface roughness and high transmittance, and can be widely used for preparing heterojunction solar cells, displays or optical components and the like.

Description

IWZO target material and preparation method and application thereof

Technical Field

The invention relates to the technical field of semiconductor materials, in particular to an IWZO target material and a preparation method and application thereof.

Background

The indium oxide doped tungsten oxide (IWO) target is an N-type semiconductor material formed by solid solution of tungsten trioxide in indium trioxide, has the characteristics of high near-infrared transmittance and mobility and small grain size of the prepared IWO film, and can be applied to a heterojunction cell as a TCO film of the N pole of the heterojunction cell.

In the related art, in: the W atomic ratio is usually between 1; if the doping concentration of tungsten oxide in indium oxide is increased, the tungsten oxide is volatile, which may cause difficulty in forming a solid solution in the target manufacturing process.

Therefore, it is highly desirable to find a highly doped tungsten oxide target material which can improve the abnormal coarsening and protrusion of the film layer caused by the too low doping concentration of tungsten and the excessive surface roughness, and the oxide film prepared by using the target material has excellent conductivity and transmittance.

Disclosure of Invention

The present invention is directed to solving at least one of the problems of the prior art. Therefore, the IWZO target material and the preparation method and application thereof are provided, the target material is high in relative density and good in color uniformity, and an oxide film prepared from the target material is low in surface roughness and has excellent conductivity and light transmittance.

The invention provides a preparation method of an IWZO target.

The invention also provides an oxide film.

The invention also provides an application of the IWZO oxide target or the oxide film in preparation of a heterojunction solar cell, a display or an optical element.

The first aspect of the invention provides an IWZO target material, comprising In, W, zn, O, in atomic molar ratio: in: w: zn =1: n: n is multiplied by M;

wherein N is more than or equal to 0.02 and less than 0.0721;

m is more than or equal to 0.8 and less than 1.2.

The IWZO target material provided by the embodiment of the invention has the following beneficial effects: according to the invention, a certain amount of zinc oxide and tungsten oxide are additionally doped into the indium oxide low-doped tungsten oxide target material, the zinc oxide is dissolved into the indium oxide in a solid solution manner to be beneficial to the solid solution of the tungsten oxide, the target material is sintered to be compact, and the density of the manufactured target material is more than 97%. The oxide target material manufactured by the invention has good uniformity, does not nodulate in the continuous use process, and does not generate point discharge.

According to some embodiments of the invention, the N satisfies 0.02495 ≦ N < 0.0721.

The second aspect of the invention provides a preparation method of an IWZO target, which comprises the following steps:

step S1: preparing indium-tungsten-zinc oxide composite powder;

step S2: carrying out spray granulation on the indium-tungsten-zinc oxide composite powder to obtain indium-tungsten-zinc oxide composite particles;

and step S3: carrying out compression molding on the indium-tungsten-zinc oxide composite particles, and carrying out cold isostatic pressing to obtain a blank target material;

and step S4: and degreasing the blank target material and then sintering to obtain the IWZO target material.

The preparation method of the IWZO target provided by the embodiment of the invention at least has the following beneficial effects:

the preparation method of the IWZO target material is beneficial to improving the solid solution of tungsten oxide, tungsten ions have certain solid solubility in indium oxide mainly under the influence of electronegativity and lattice constant, the ionic radius of zinc ions is very close to the electronegativity of indium ions, the zinc ions are easy to replace and dissolve with indium atoms, the zinc ions are divalent, one zinc ion is replaced and dissolved to obtain an anion vacancy to promote the solid solution of hexavalent tungsten ions, the charge obtained after the addition of three divalent zinc ions and one hexavalent tungsten ion is 12, and when the solid solution replaces the lattices of four trivalent indium ions, the total number of the charges is not changed by 12, and the balance of electrons is kept.

According to some embodiments of the present invention, in step S1, a specific preparation method of the indium tungsten zinc oxide composite powder includes:

step S11: mixing indium raw material liquid and zinc raw material liquid, adding a pH regulator, regulating the pH to 7.8-8.2, reacting, collecting a solid phase after the reaction is finished, drying and calcining to obtain indium zinc oxide powder;

step S12: mixing the indium-zinc oxide powder with tungsten oxide powder, and then carrying out ball milling to obtain the indium-tungsten-zinc oxide composite powder, wherein the indium-tungsten-zinc oxide composite powder comprises In, W, zn and O In terms of atomic molar ratio: in: w: zn =1: n: n is multiplied by M;

wherein N is more than or equal to 0.02 and less than 0.0721;

m is more than or equal to 0.5 and less than 1.2.

According to the invention, by controlling the preparation method of the target material powder and adopting a coprecipitation method to prepare the indium zinc oxide powder, the uniformity problem of the target material is solved, and the doping concentration of tungsten is improved.

According to some embodiments of the present invention, the solute of the indium raw material liquid includes at least one of indium sulfate, indium nitrate, and indium chloride, and a molar concentration of indium in the indium raw material liquid is 0.05mol/L to 0.3mol/L;

preferably, the solute of the zinc raw material solution comprises at least one of zinc sulfate, zinc nitrate and zinc chloride, and the molar concentration of zinc in the zinc raw material solution is 0.05 mol/L-0.3 mol/L.

According to some embodiments of the invention, in the step S11, the reaction temperature is 20 ℃ to 45 ℃ and the calcination temperature is 600 ℃ to 950 ℃.

According to some embodiments of the invention, the tungsten oxide powder has a specific surface area of 12m or more ² /g。

According to some embodiments of the invention, the method of preparing the tungsten oxide powder comprises: carrying out hydrothermal treatment on the tungsten raw material liquid, collecting a solid phase, drying and calcining to obtain tungsten oxide powder;

preferably, the solute of the tungsten raw material solution includes at least one of sodium tungstate, ammonium tungstate and potassium tungstate;

preferably, the molar concentration of indium in the indium raw material liquid is 0.05mol/L to 0.3mol/L;

preferably, the calcination temperature of the solid phase obtained by the reaction of the tungsten raw material liquid is 400-900 ℃.

According to some embodiments of the invention, D of the indium tungsten zinc oxide composite particles ₅₀ 5 to 15 μm.

According to some embodiments of the invention, the compression molding pressure in step S3 is 0.1Mpa to 0.8Mpa.

According to some embodiments of the invention, the cold isostatic pressure in step S3 is between 200MPa and 400MPa.

According to some embodiments of the invention, in the step S3, the heat treatment temperature for degreasing is 350 ℃ to 700 ℃;

preferably, the temperature rise speed of the degreasing is 0.5-2 ℃/min;

preferably, the degreasing treatment time is 3-6 h.

According to some embodiments of the invention, in step S3, the sintering temperature is 1000 ℃ to 1500 ℃;

preferably, the temperature rise speed of the sintering is 0.5-5 ℃/min;

preferably, the cooling speed of the sintering is 5-10 ℃/min;

preferably, the sintering time is 5-8 h.

The third aspect of the invention provides an oxide film, which is prepared by adopting the IWZO target material through a sputtering deposition process or an evaporation deposition process;

preferably, the sputtering deposition process comprises the steps of installing the IWZO target on a magnetron sputtering target position, and then adjusting the vacuum in a magnetron sputtering cavity to be less than 8 x 10 ^-4 Pa, and carrying out magnetron sputtering on the substrate to obtain the material;

preferably, the atmosphere in the magnetron sputtering process is argon atmosphere or argon and oxygen mixed atmosphere;

preferably, the target surface magnetic field intensity of the IWZO target in the magnetron sputtering process is 300 Gs-1000 Gs.

The oxide thin film according to the embodiment of the invention has at least the following beneficial effects: the oxide film of the invention has low resistivity (the resistivity is less than or equal to 9.00 multiplied by 10) ^-4 Omega cm), and on the premise of not influencing the conductivity of the film, the crystal grains of the film are refined, and the roughness of the film is reduced.

According to some embodiments of the present invention, when the atmosphere in the magnetron sputtering process is a mixed atmosphere of argon and oxygen, the ratio by volume of argon: oxygen =100:0 to 2.

Preferably, the purity of the argon gas is not less than 99.99%.

Preferably, the purity of the oxygen is not less than 99.99%.

According to some embodiments of the invention, a sputtering gas pressure during the magnetron sputtering is 0.05Pa to 1Pa.

According to some embodiments of the invention, the magnetron sputtering may employ direct current magnetron sputtering, direct current pulse magnetron sputtering, medium frequency magnetron sputtering, or DC + RF magnetron sputtering.

According to some embodiments of the invention, the power source for magnetron sputtering is a dc power source.

According to some embodiments of the invention, the magnetron sputtering has a power of 0.5w/cm ² ～3.5w/cm ² 。

Preferably, the magnetron sputtering isThe power is 0.75W/cm ² ～1.5W/cm ² ；

Preferably, the power of the magnetron sputtering is 1.0w/cm ² 。

According to some embodiments of the present invention, the evaporation Deposition may be performed by electron gun evaporation or Reactive Plasma evaporation (RPD).

According to some embodiments of the invention, the vapor deposition chamber has a pressure of 2.0 × 10 ^-6 ～7.5×10 ^- ⁶ Torr。

The invention provides an application of the IWZO target material in preparation of a heterojunction solar cell, a display or an optical component.

Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.

Drawings

The invention is further described with reference to the following figures and examples, in which:

FIG. 1 is a view showing the target surface of an IWZO target obtained in example 1 of the present invention after sputtering;

FIG. 2 is a view showing the target surface of an IWZO target obtained in comparative example 2 of the present invention after sputtering.

Detailed Description

The idea of the invention and the resulting technical effects will be clearly and completely described below in connection with the embodiments, so that the objects, features and effects of the invention can be fully understood. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts are within the protection scope of the present invention based on the embodiments of the present invention.

In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.

Example 1

The embodiment is an IWZO target and a preparation method thereof, and the preparation method comprises the following steps:

s1, carrying out hydrothermal treatment on a sodium tungstate solution with the concentration of 0.2mol/L for 6 hours, collecting a solid phase, washing, and then carrying out freeze drying; calcining for 1h at 580 ℃ to obtain the tungsten oxide powder.

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the In: zn atomic ratio =1:0.02495 x 1, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball-milling circulation on the reaction solution In the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing the tungsten oxide powder and the indium zinc oxide powder according to the atomic ratio of In: W: zn =1:0.02495:0.02495 x 1, wherein the tungsten oxide powder has a specific surface area of 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

S4, carrying out spray granulation on the indium-tungsten-zinc oxide composite powder to obtain indium-tungsten-zinc oxide particles, D ₅₀ Is 10 μm.

S5, carrying out compression molding on the indium-tungsten-zinc oxide particles under the pressure of 0.4MPa, and carrying out cold isostatic pressing after compression molding, wherein the pressure is 350MPa, so as to obtain a blank target material.

S6, degreasing the blank target at 600 ℃, and sintering at 1300 ℃ after degreasing to obtain an IWZO target; wherein the heating rate of the degreasing temperature is 1 ℃/min, and the degreasing temperature is kept for 5h after being heated to 600 ℃; the temperature rise speed of sintering is 2 ℃/min; heating to 1300 deg.C, maintaining for 6h, and cooling at 7 deg.C/min.

The specific method for preparing the oxide film by using the IWZO target comprises the following steps:

step S1, processing the IWZO target into a target for magnetron sputtering equipment;

s2, mounting the target material on a magnetron sputtering target position, wherein the magnetic field intensity of the target surface is about 500Gs, and the background vacuum pressure of a vacuum chamber is less than 8 multiplied by 10 ^-4 Pa, substrate temperature of about 170 ℃, introducing Ar gas (purity 99.99%) and oxygen (purity 99.99%), the volume ratio of the gas is 100/0.2, the pressure of the vacuum chamber is about 0.25Pa, sputtering by using a direct current power supply, and the sputtering power is 1.0w/cm ² And depositing a film layer with the thickness of about 100nm on the substrate.

Example 2

The embodiment provides an IWZO target and a preparation method thereof, which comprises the following steps:

s1, carrying out hydrothermal treatment on a sodium tungstate solution with the concentration of 0.2mol/L for 6 hours, collecting a solid phase, washing, and then carrying out freeze drying; calcining for 1h at 770 ℃ to obtain the tungsten oxide powder.

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the atomic ratio of In to Zn =1 of 0.02495 x 1, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball milling circulation on the reaction solution during the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to the atomic ratio of In, W and Zn =1:0.02495:0.02495 x 1, wherein the specific surface area of the tungsten oxide powder is 12m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

S4, carrying out spray granulation on the indium-tungsten-zinc oxide composite powder to obtain indium-tungsten-zinc oxide particles D ₅₀ Is 10 μm.

S6, degreasing the blank target material at 600 ℃, and sintering at 1300 ℃ after degreasing to obtain an IWZO target material; wherein the heating rate of the degreasing temperature is 1 ℃/min, and the degreasing temperature is kept for 5h after being heated to 600 ℃; the temperature rise speed of sintering is 2 ℃/min; heating to 1300 deg.C, maintaining for 6h, and cooling at 7 deg.C/min.

s1, processing the IWZO target into a target for magnetron sputtering equipment;

s2, mounting the target material on a magnetron sputtering target position, wherein the magnetic field intensity of the target surface is about 500Gs, and the background vacuum pressure of a vacuum chamber is less than 8 multiplied by 10 ^-4 Pa, substrate temperature of about 170 ℃, introducing Ar gas (purity 99.99%) and oxygen (purity 99.99%), the volume ratio of the gas is 100/0.2, the pressure of the vacuum chamber is about 0.25Pa, sputtering by using a direct current power supply, and the sputtering power is 1.0w/cm ² And depositing a film layer of about 100nm on the substrate.

Example 3

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the atomic ratio of In to Zn =1:0.0521 × 1.19, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball milling circulation on the reaction solution during the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to the atomic ratio of In: W: zn =1:0.0521 × 1.19 mixing, wherein oxidizingThe specific surface area of the tungsten powder is 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

S5, carrying out compression molding on the indium-tungsten-zinc oxide particles under the pressure of 0.4MPa, and carrying out cold isostatic pressing after compression molding, wherein the pressure is 350MPa, thus obtaining the blank target material.

Example 4

s1, carrying out hydrothermal treatment on a sodium tungstate solution with the concentration of 0.2mol/L for 6 hours, collecting a solid phase, washing, and then carrying out freeze drying; calcining at 580 deg.C for 1h to obtain tungsten oxide powder.

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the atomic ratio of In to Zn =1 of 0.0521, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball milling circulation on the reaction liquid during the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to an In: W: zn atomic ratio =1:0.0521 × 1 mixing, wherein the specific surface area of the tungsten oxide powder is 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

s2, mounting the target material on a magnetron sputtering target position, wherein the magnetic field intensity of the target surface is about 500Gs, the background vacuum pressure of a vacuum chamber is less than 8 multiplied by 10 ^-4 Pa, substrate temperature of about 170 ℃, introducing Ar gas (purity 99.99%) and oxygen (purity 99.99%), the volume ratio of the gas is 100/0.2, the pressure of the vacuum chamber is about 0.25Pa, sputtering by using a direct current power supply, and the sputtering power is 1.0w/cm ² And depositing a film layer with the thickness of about 100nm on the substrate.

Example 5

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the atomic ratio of In to Zn =1:0.0521 x 0.8, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball-milling circulation on a reaction solution In the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to the atomic ratio of In: W: zn =1:0.0521 × 0.8, wherein the specific surface area of the tungsten oxide powder is 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

Example 6

s1, carrying out hydrothermal treatment on a sodium tungstate solution with the concentration of 0.2mol/L for 6 hours, collecting a solid phase, washing, and freeze-drying; calcining for 1h at 580 ℃ to obtain the tungsten oxide powder.

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the atomic ratio of In to Zn =1 of 0.02495 to 1.19, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball-milling circulation on the reaction solution during the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to the atomic ratio of In, W and Zn =1:0.02495:0.02495 × 1.19, wherein the tungsten oxide powder has a specific surface area of 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

s2, mounting the target material on a magnetron sputtering target position, wherein the magnetic field intensity of the target surface is about 500Gs, the background vacuum pressure of a vacuum chamber is less than 8 multiplied by 10 ^-4 Pa, substrate temperatureAbout 170 ℃, introducing Ar gas (with the purity of 99.99%) and oxygen gas (with the purity of 99.99%), wherein the volume ratio of the gases is 100/0.2, the pressure of a vacuum chamber is about 0.25Pa, sputtering by using a direct current power supply, and the sputtering power is 1.0w/cm ² And depositing a film layer with the thickness of about 100nm on the substrate.

Example 7

s1, carrying out hydrothermal treatment on a sodium tungstate solution with the concentration of 0.2mol/L for 6 hours, collecting a solid phase, washing, and freeze-drying; calcining at 580 deg.C for 1h to obtain tungsten oxide powder.

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the atomic ratio of In to Zn =1 of 0.02495 to 0.8, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball-milling circulation on the reaction solution during the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to the atomic ratio of In, W and Zn =1:0.02495:0.02495 × 0.8, wherein the specific surface area of the tungsten oxide powder is 15m ² And/g, mixing and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

Example 8

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the atomic ratio of In to Zn = 1.02 to 1.19, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball milling circulation on the reaction solution during the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to the atomic ratio of In, W and Zn =1:0.02:0.02 x 1.19, wherein the tungsten oxide powder has a specific surface area of 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

And S4, carrying out spray granulation on the indium-tungsten-zinc oxide composite powder to obtain indium-tungsten-zinc oxide particles, wherein D50 is 10 microns.

s2, mounting the target material on a magnetron sputtering target position, wherein the magnetic field intensity of the target surface is about 500Gs, the background vacuum pressure of a vacuum chamber is less than 8 multiplied by 10 ^-4 Pa, substrate temperature of about 170 ℃, introducing Ar gas (purity 99.99%) and oxygen (purity 99.99%), the volume ratio of the gas is 100/0.2, the pressure of the vacuum chamber is about 0.25Pa, sputtering by using a direct current power supply, and the sputtering power is 1.0w/cm ² And depositing a film layer of about 100nm on the substrate.

Example 9

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the atomic ratio of In to Zn = 1.02 to 1.0, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball-milling circulation on the reaction liquid In the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to the atomic ratio of In: W: zn =1:0.02:0.02 x 1.0, wherein the tungsten oxide powder has a specific surface area of 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

Example 10

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the atomic ratio of In to Zn =1 of 0.02 to 0.8, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball milling circulation on the reaction solution during the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to the atomic ratio of In, W and Zn =1:0.02:0.02 x 0.8 mixing, wherein oxidizingThe specific surface area of the tungsten powder is 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

Comparative example 1

s1, carrying out hydrothermal treatment on a sodium tungstate solution with the concentration of 0.2mol/L for 6 hours, collecting a solid phase, washing, and freeze-drying; calcining for 1h at 950 ℃ to obtain the tungsten oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to the atomic ratio of In, W and Zn =1:0.02495:0.02495 x 1, wherein the specific surface area of the tungsten oxide powder is 8m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

Comparative example 2

The comparative example is a preparation method of an IWZO target and an oxide film, and comprises the following steps:

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the In: zn atomic ratio =1:0.0721 x 3, adjusting the pH value to 8.1 for reaction by dropwise adding a sodium hydroxide solution, controlling the reaction temperature to be about 30 ℃, performing ball milling circulation on the reaction solution In the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to the atomic ratio of In, W and Zn =1:0.0721 × 3 mixing, wherein the specific surface area of the tungsten oxide powder is 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

Comparative example 3

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the atomic ratio of In to Zn =1 of 0.0521 × 3, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball milling circulation on the reaction liquid during the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to an In: W: zn atomic ratio =1:0.0521 × 3, wherein the tungsten oxide powder has a specific surface area of 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

Comparative example 4

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the atomic ratio of In to Zn =1 of 0.0521 × 2.5, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball milling circulation on the reaction solution during the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to an In: W: zn atomic ratio =1:0.0521 × 2.5, wherein the tungsten oxide powder has a specific surface area of 15m ² And/g, mixing and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

Comparative example 5

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the atomic ratio of In to Zn =1:0.0521 × 1.5, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball milling circulation on the reaction solution during the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to an In: W: zn atomic ratio =1:0.0521 to 1.5, wherein the tungsten oxide powder has a specific surface area of 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

s2, mounting the target material on a magnetron sputtering target position, wherein the magnetic field intensity of the target surface is about 500Gs, and the background vacuum pressure of a vacuum chamber is less than 8 multiplied by 10 ^-4 Pa, the temperature of the substrate is about 170 ℃, ar gas (with the purity of 99.99%) and oxygen gas (with the purity of 99.99%) are introduced, the volume ratio of the gas is 100/0.2, the pressure of the vacuum chamber is about 0.25Pa, a direct current power supply is used for sputtering, the sputtering power is 1.0w/cm < 2 >, and a film layer with the thickness of about 100nm is deposited on the substrate.

Comparative example 6

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the atomic ratio of In to Zn =1 of 0.0521 to 0.5, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball milling circulation on the reaction solution during the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder according to an In: W: zn atomic ratio =1:0.0521 × 0.5, wherein the tungsten oxide powder has a specific surface area of 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

Comparative example 7

The comparative example is a preparation method of an IWZO target and an oxide film, which comprises the following steps:

S2, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L according to the In: zn atomic ratio =1:0.006048 × 1, adjusting the pH value to 8.1 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, performing ball milling circulation on the reaction liquid In the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain indium zinc oxide powder.

S3, mixing tungsten oxide powder and indium zinc oxide powder,according to the atomic ratio of In, W and Zn =1:0.006048:0.006048 mixed, wherein the specific surface area of the tungsten oxide powder is 15m ² And/g, mixing and performing ball milling for 20 hours to obtain the indium-tungsten-zinc oxide composite powder.

Comparative example 8

The comparative example is an indium tungsten oxide target, wherein the atomic ratio of In to W is = 1.0721, and the preparation method of the target and the oxide film comprises the following steps:

S2, dropwise adding a sodium hydroxide solution into an indium chloride solution with the concentration of 0.2mol/L to adjust the pH value to 8.1 for reaction, controlling the reaction temperature to be about 30 ℃, performing ball milling circulation on reaction liquid during the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 ℃ for 1h to obtain the indium oxide powder.

S3, mixing tungsten oxide powder and indium oxide powder according to the atomic ratio of In to W =1:0.0721, wherein the specific surface area of the tungsten oxide powder is 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten oxide composite powder.

S4, carrying out spray granulation on the indium-tungsten oxide composite powder to obtain indium-tungsten oxide particles, D ₅₀ Is 10 μm.

S5, carrying out compression molding on the indium tungsten oxide particles under the pressure of 0.4MPa, and carrying out cold isostatic pressing after compression molding, wherein the pressure is 350MPa, so as to obtain a blank target material.

S6, degreasing the blank target material at 600 ℃, and sintering the degreased blank target material at 1300 ℃ to obtain an indium tungsten oxide target material; wherein the heating rate of the degreasing temperature is 1 ℃/min, and the degreasing temperature is kept for 5h after being heated to 600 ℃; the temperature rise speed of sintering is 2 ℃/min; heating to 1300 deg.C, maintaining for 6h, and cooling at 7 deg.C/min.

The specific method for preparing the oxide film by using the indium-tungsten oxide target material comprises the following steps:

s1, processing the indium tungsten oxide target into a target for magnetron sputtering equipment;

s2, mounting the target material on a magnetron sputtering target position, wherein the magnetic field intensity of the target surface is about 500Gs, and the background vacuum pressure of a vacuum chamber is less than 8 multiplied by 10 ^-4 Pa, substrate temperature of about 170 ℃, introducing Ar gas (purity 99.99%) and oxygen (purity 99.99%), the volume ratio of the gas is 100/0.2, the pressure of the vacuum chamber is about 0.25Pa, sputtering by using a direct current power supply, and the sputtering power is 1.0w/cm ² And arcing is serious in the sputtering process, and a sample is not manufactured.

Comparative example 9

The comparative example is an indium tungsten oxide target, wherein the atomic ratio of In to W is = 1.0521, and the preparation method of the target and the oxide film comprises the following steps:

S2, adding a sodium hydroxide solution dropwise into an indium chloride solution with the concentration of 0.2mol/L to adjust the pH value to 8.1 for reaction, controlling the reaction temperature to be about 30 ℃, performing ball milling circulation on reaction liquid during the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 ℃ for 1h to obtain the indium oxide powder.

S3, mixing tungsten oxide powder and indium oxide powder according to an In: W atomic ratio =1:0.0521, wherein the tungsten oxide powder has a specific surface area of 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten oxide composite powder.

S6, degreasing the blank target at 600 ℃, and sintering at 1300 ℃ after degreasing to obtain an indium-tungsten oxide target; wherein the heating rate of the degreasing temperature is 1 ℃/min, and the degreasing temperature is kept for 5h after being heated to 600 ℃; the temperature rise speed of sintering is 2 ℃/min; heating to 1300 deg.C, maintaining for 6h, and cooling at 7 deg.C/min.

Comparative example 10

The comparative example is an indium tungsten oxide target material, wherein the atomic ratio of In to W is = 1.02495, and the preparation method of the target material and the oxide film comprises the following steps:

S3, mixing tungsten oxide powder and indium oxide powder according to the atomic ratio of In to W =1:0.02495, wherein the specific surface area of the tungsten oxide powder is 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten oxide composite powder.

S5, carrying out compression molding on the indium tungsten oxide particles under the pressure of 0.4MPa, and carrying out cold isostatic pressing after compression molding, wherein the pressure is 350MPa, thus obtaining the blank target material.

s2, mounting the target material on a magnetron sputtering target position, wherein the magnetic field intensity of the target surface is about 500Gs, and the background vacuum pressure of a vacuum chamber is less than 8 multiplied by 10 ^-4 Pa, substrate temperature of about 170 DEG COn the right, ar gas (purity 99.99%) and oxygen (purity 99.99%) are introduced, the volume ratio of the gas is 100/0.2, the pressure of the vacuum chamber is about 0.25Pa, the sputtering is carried out by using a direct current power supply, and the sputtering power is 1.0w/cm ² And depositing a film layer of about 100nm on the substrate.

Comparative example 11

The comparative example is an indium tungsten oxide target, wherein the atomic ratio of In to W is = 1.02, and the preparation method of the target and the oxide film comprises the following steps:

S3, mixing tungsten oxide powder and indium oxide powder according to an In: W atomic ratio =1:0.02 mixing, wherein the specific surface area of the tungsten oxide powder is 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten oxide composite powder.

Comparative example 12

The comparative example is an indium tungsten oxide target material, wherein the atomic ratio of In to W is =1, and the preparation method of the target material and the oxide film comprises the following steps:

S3, mixing tungsten oxide powder and indium oxide powder according to an In: W atomic ratio =1:0.006048, wherein the specific surface area of the tungsten oxide powder is 15m ² And/g, mixing, and performing ball milling for 20 hours to obtain the indium-tungsten oxide composite powder.

Example of detection

The performance of the target and the oxide film prepared in the embodiments 1 to 10 and the comparative examples 1 to 12 are respectively tested in the test example, wherein the performance test specifically comprises the following steps:

(1) Relative density of oxide target: the density was measured by the archimedes method, and the ratio (%) thereof to a reference density determined from the composition was determined as a relative density.

(2) Thickness of oxide film: the measurement was carried out using a step apparatus manufactured by Bruker, model Dektak150.

(3) Surface roughness of oxide film: the measurement is carried out by an atomic force microscope, the manufacturer of the atomic force microscope is a fine work, and the model is SPA400.

(4) Transmittance of oxide thin film layer: the ultraviolet-visible-infrared spectrophotometer was manufactured by Shimadzu and was UV-3600i.

(5) Resistivity of oxide film: and (3) calculating the resistivity according to the thickness of the film and the sheet resistance, wherein the sheet resistance is measured at room temperature by using a four-probe method, and the manufacturer of the four-probe resistance tester is Mitsubishi and the model is MCP-T360.

Specific detection results of the oxide targets prepared in examples 1 to 10 and comparative examples 1 to 12 of the present invention are shown in table 1:

table 1: statistics of oxide targets obtained in examples 1 to 10 and comparative examples 1 to 12

As can be seen from the above Table 1, compared with the oxide targets not doped with Zn element (comparative examples 8 to 12), the IWZO targets prepared by the invention have high relative density and uniform target surface color, and the sputtering runways are smooth after sputtering by the magnetron sputtering process.

Among them, as can be analyzed from examples 1 to 2 and comparative example 1, the relative density of the oxide target decreases as the specific surface area of the tungsten oxide powder decreases, mainly because the specific surface area of the tungsten oxide powder is too small to facilitate sintering of the target, and thus the sintering density is low. The condition of the target surface of the target prepared in the embodiment 1 after sputtering is shown in fig. 1, and it can be seen from fig. 1 that the target surface is smooth and uniform in color, and no cracking phenomenon occurs.

It can be analyzed from examples 1, 3 to 10 and comparative examples 2 to 12 that the solid solution of zinc oxide into indium oxide is advantageous to promote the solid solution of tungsten oxide, so that the oxide target material is sintered densely. In comparative example 2, in: w: zn atomic ratio =1: n: n × M =1:0.072100:0.072100 x 3, that is, when zinc atoms doped in indium oxide is 3 times of tungsten atoms, compared to examples 1 to 10 and comparative example 3, the relative density of the target is significantly reduced, and the sputtering track of the target is rough, as shown in fig. 2, which is mainly due to the excessive amount of tungsten oxide doped in indium oxide, which is volatile, so that solid solution is difficult to form during the target manufacturing process; when no zinc oxide was added, the target relative density further decreased as shown in comparative example 8.

It can be analyzed from examples 1, 3 to 10 and comparative examples 2 to 12 that the solid solution of zinc oxide into indium oxide is advantageous in promoting the solid solution of tungsten oxide, making the oxide target sintered densely, and the sintered density of the target increased as the proportion of zinc atoms incorporated increases. When the proportion of doped zinc atoms is too low, the density of the manufactured target is low, and M is limited to be more than or equal to 0.8 in order to ensure the density of the indium-tungsten-zinc oxide target.

Further, the detailed examination of the oxide thin films obtained in examples 1 to 10 of the present invention and comparative examples 1 to 12 is shown in Table 2.

Table 2: results of measuring Properties of oxide films obtained in examples 1 to 10 and comparative examples 1 to 12

As can be seen from table 2, as the doping ratio of tungsten atoms increases, the resistivity of the deposited film decreases (as shown in examples 1, 3 to 10 and comparative examples 8 to 12), mainly because the doping of tungsten atoms to form indium lattice vacancies can additionally dope zinc atoms, doped zinc tungsten atoms, one formed hole, one formed electron. The conductivity of the deposited film is controlled by controlling the proportion of zinc-tungsten atoms doped in the indium oxide.

Next, as can be analyzed from examples 1, 3 to 10 and comparative examples 2 to 5, the resistivity of the deposited film layer increased as the doping ratio of zinc atoms increased. As shown in comparative examples 2 and 3, the zinc ions doped in the indium oxide are 3 times of the tungsten ions, and after the zinc ions and the tungsten ions are dissolved in the indium oxide crystal lattice, the generated holes and electrons are mutually counteracted, thereby causing the electrical conductivity of the deposited film layer to be sharply reduced. In order to ensure good conductivity of the deposited film, the doping amount of zinc needs to be controlled, and M is limited to be less than 1.2.

Further, it can be seen from table 2 that indium oxide doped with zinc oxide and tungsten oxide, as the doping ratio of tungsten oxide increases, the surface roughness of the deposited film decreases, but the roughness decreases less significantly (as in examples 3, 6 and 8). When the amount of tungsten oxide is fixed, the grains of the deposited film are refined and the surface roughness of the film is reduced along with the increase of the proportion of the doped zinc oxide. When the proportion of the tungsten oxide doped with indium oxide is lower (as in comparative examples 7 and 12), although the surface roughness of the film is obviously reduced with the doping of zinc oxide, the surface roughness of the film is still higher, so that the N is limited to be more than or equal to 0.02 in order to reduce the surface roughness of the deposited film.

In summary, the invention is based on an indium oxide low-doped tungsten oxide target material, and the In: w: zn atomic ratio =1: n: n x M ratio (0.02N < 0.0721, 0.8M < 1.2) to obtain an indium oxide highly doped tungsten oxide target material, which has at least the following advantages:

(1) The invention solves the problems of uniformity of zinc in indium oxide and uniformity of target material by adopting a preparation method of controlling target material powder by adopting coprecipitation to prepare indium zinc oxide powder.

(2) According to the invention, a certain amount of zinc oxide is additionally doped into the indium oxide low-doped tungsten oxide target material, and tungsten atoms are doped to form an indium crystal lattice vacancy, so that zinc atoms, doped zinc tungsten atoms, a formed hole and a formed electron can be additionally doped, thereby solving the problem of poor solid solubility of the low-doped tungsten oxide target material.

(3) The invention controls the conductivity of the deposited film by controlling the proportion of zinc-tungsten atoms doped in the indium oxide, so that the resistivity of the film is less than or equal to 9.00 multiplied by 10 ^-4 Omega cm. The solid solution of zinc oxide into indium oxide is beneficial to the solid solution of tungsten oxide, the sintering of the target material is compact, and the density of the manufactured target material is more than 97 percent. The indium oxide low-doped tungsten oxide target is additionally doped with zinc oxide, so that the total doping amount of tungsten oxide can be increased, the grains of the deposited film are refined, and the surface roughness of the film is reduced.

(4) The IWZO target material prepared by the method has good uniformity, does not generate nodulation and point discharge in the continuous use process, and can be widely used for preparing heterojunction solar cells, displays or optical components and the like.

The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.

Claims

1. An IWZO target comprising In, W, zn, O, in: w: zn =1: n: n × M;

wherein N is more than or equal to 0.02 and less than 0.0721;

m is more than or equal to 0.8 and less than 1.2.

2. The method for preparing the IWZO target material of claim 1, comprising the steps of:

step S1: preparing indium-tungsten-zinc oxide composite powder;

3. The method according to claim 2, wherein in step S1, the specific preparation method of the indium tungsten zinc oxide composite powder comprises:

step S12: mixing the indium zinc oxide powder and the tungsten oxide powder and then carrying out ball milling to obtain the indium zinc oxide powder.

4. The method according to claim 3, wherein the solute of the indium raw material liquid includes at least one of indium sulfate, indium nitrate, and indium chloride, and a molar concentration of indium in the indium raw material liquid is 0.05mol/L to 0.3mol/L;

5. The method according to claim 3, wherein the specific surface area of the tungsten oxide powder is not less than 12m ² /g。

6. The method according to any one of claims 2 to 5, wherein in step S3, the pressure for the compression molding is 0.1MPa to 0.8MPa;

preferably, the pressure of the cold isostatic pressing is 200 MPa-400 MPa;

preferably, the heat treatment temperature of the degreasing is 400-700 ℃;

preferably, the sintering temperature is 1000-1500 ℃.

7. An oxide thin film, which is prepared by the IWZO target material according to claim 1 through a sputtering deposition process or an evaporation deposition process;

preferably, the sputtering deposition process comprises the steps of installing the IWZO target on a magnetron sputtering target position, and then adjusting the vacuum in a magnetron sputtering cavity to be less than 8 x 10 ^-4 Pa, and carrying out magnetron sputtering on the base material to obtain the material.

8. The oxide thin film according to claim 7, wherein an atmosphere during the magnetron sputtering is an argon atmosphere or a mixed atmosphere of argon and oxygen;

9. The oxide thin film according to claim 8, wherein the oxide thin film has a resistivity of 9.00 x 10 or less ^-4 Ω.cm。

10. Use of the IWZO target according to claim 1 or the oxide thin film according to any one of claims 8 to 9 for the production of a heterojunction solar cell, a display or an optical component.