TWI765654B - Composite ceramic sputtering target, method of preparing the same, and composite ceramic film and method of preparing the same - Google Patents

Abstract

The present invention provides a composite ceramic sputtering target, and the composite ceramic sputtering target includes a first metal oxide, a second metal oxide and a metal. A number of crystallization phase of the composite ceramic sputtering target is two; and based on the total weight of the composite ceramic sputtering target, an amount of the metal is more than or equal to 0.3 wt% and less than or equal to 30 wt%, and an amount of the second metal oxide is more than or equal to 0.5 wt% and less than or equal to 2 wt%. The composite ceramic sputtering target of the present invention has high relative density, and the metal has better dispersion uniformity and smaller grain size, which can improve the quality of the composite ceramic film made from the composite ceramic sputtering target, and also can simplify the preparing process of the composite ceramic film.

Description

Composite ceramic target, method for making the same, and composite ceramic film and method for making the same

This creation relates to a target, its manufacturing method, a thin film formed by sputtering and its manufacturing method, especially a composite ceramic target, its manufacturing method, a composite ceramic thin film formed by its sputtering, and its manufacturing method.

With the increasing attention to environmental safety and air quality, the technological development related to gas sensors has also received attention. A gas sensor is a device that can detect gas molecules in the air and convert them into electrical signals. Therefore, it has been widely used in the detection of flammable and explosive gases such as hydrogen, methane or natural gas in the air. Or gases such as hydrogen sulfide, sulfur dioxide or chlorine that are harmful to human health.

Gas sensors can be classified into different types according to different working principles, such as semiconductor gas sensors, electrochemical gas sensors, and catalytic combustion gas sensors. Among the types of semiconductor gas sensors, metal oxide semiconductors have become one of the most commonly used types of gas sensors for gas detection due to their sensitive detection response and relatively low cost.

Metal oxides such as zinc oxide, tin oxide, etc., have semiconductor properties due to their special structures. Therefore, when gas molecules are adsorbed on the surface of the film made of metal oxides, their original conductive properties will be changed. The concentration of adsorbed gas molecules can be obtained by measuring the change of the resistance value of the metal oxide film; in addition, in order to further improve the sensitivity of the detection reaction, various metal elements such as platinum, palladium, copper, gold, etc. are usually selected and metal oxides together to form a thin film, thereby optimizing the performance of the gas sensor.

At present, the technical means used to form thin films with metal elements and metal oxides include spin coating, co-precipitation, and sol-gel methods and other non-physical vapor deposition (Physical Vapor Deposition, PVD) preparation methods. The quality of the films produced by the aforementioned non-PVD process is relatively poor and it is difficult to maintain good stability; however, if the film is prepared by co-sputtering with a metal element target and a metal oxide target, it is necessary to use a DC magnetron at the same time. Sputtering (DC magnetron sputtering) and radio-frequency magnetron sputtering (Radio-Frequency magnetron sputtering) two sputtering methods not only increase the complexity of the preparation process, but also have uneven distribution of metal elements mixed in the film. The problem of cracks in the film caused by the large particle size affects the application of subsequent gas detection.

In view of the defects faced by the prior art, the purpose of this creation is to provide a composite ceramic target material containing an additive metal, and the additive metal in the composite ceramic target material has better dispersion uniformity and smaller particle size, and further It can improve the quality of the thin film formed by sputtering and simplify the process of thin film at the same time, so as to facilitate the application of subsequent gas detection.

In order to achieve the aforementioned object, the present invention provides a composite ceramic target material, which comprises a first metal oxide, a second metal oxide and an additive metal, the number of crystal phases of the composite ceramic target material is two phases, and the Based on the total weight of the composite ceramic target, the content of the added metal is greater than or equal to 0.3 weight percent (weight percentage, wt %) and less than or equal to 30 wt %, and the content of the second metal oxide is greater than or equal to 0.5 wt % and less than or equal to 2 wt %; wherein, the first metal oxide comprises tin dioxide (SnO ₂ ), titanium dioxide (TiO ₂ ), zinc monoxide (ZnO), indium trioxide (In ₂ O _{3 )} ), molybdenum trioxide (MoO ₃ ), tungsten trioxide (WO ₃ ), zirconium dioxide (ZrO ₂ ) or a combination thereof, the second metal oxide comprises copper monoxide (CuO), antimony trioxide (Sb ₂ ) O ₃ ), cobalt monoxide (CoO), manganese dioxide (MnO ₂ ) or a combination thereof, the additive metal includes palladium (Pd), platinum (Pt), ruthenium (Ru), gold (gold) , Au), silver (silver, Ag), indium (indium, In) or a combination thereof.

Accordingly, by controlling the number of crystal phases of the composite ceramic target and the contents of the second metal oxide and the additive metal, the composite ceramic target can have a higher relative density and the additive metal has a better The dispersion uniformity and the smaller particle size of the composite ceramic film can form a good quality composite ceramic film with uniform dispersion of the added metal, small particle size and no cracks, which is beneficial to the application of subsequent gas detection; in addition, the composite ceramic film provided by this creation The ceramic target contains a single target with added metal and metal oxide at the same time, so it can avoid the problem of selecting two different materials for the target and adjusting the process parameters separately, such as co-sputtering or co-evaporation. The advantages of the ceramic thin film process.

According to the present invention, the first metal oxide is the main component in the composite ceramic target; it should be understood that the composite ceramic target does not only contain the first metal oxide, the second metal oxide and the additive Metal, on the premise that the effect of the present invention is not affected, the composite ceramic target may contain other components besides the first metal oxide, the second metal oxide and the additive metal.

In an embodiment of the present invention, the relative density of the composite ceramic target is greater than or equal to 60%. In this embodiment, the composite ceramic target can be used for the deposition process to prepare the composite ceramic thin film. In another embodiment of the present invention, the relative density of the composite ceramic target is greater than or equal to 95%. In this embodiment, the composite ceramic target can be used in a sputtering process to prepare a composite ceramic thin film.

Preferably, based on the total weight of the composite ceramic target, the content of the additive metal is greater than or equal to 9 wt % and less than or equal to 15 wt %.

In an embodiment of the present invention, the first metal oxide is tin dioxide, the second metal oxide is copper monoxide, and the additive metal is palladium.

於此，該添加金屬的分散均勻度指標即代表在該複合陶瓷靶材的不同位置添加金屬重量佔比之變化率，因此該分散均勻度指標的數值越低表示該添加金屬的重量佔比變化率越小，即在複合陶瓷靶材不同位置之添加金屬的重量佔比近似，進而能夠用以評估該添加金屬於該複合陶瓷靶材中整體分散均勻的情況。舉例而言，可在靶材中心取一點與距離所述中心10公分的圓周上每隔90度各取一點，以獲得五處位置，接著以能量散射X射線譜(Energy Dispersive Spectrometer，EDS)分析所述五處位置中添加金屬之重量百分比數據，隨後將所測得五組數據中添加金屬重量百分比的最大值、最小值以及平均值代入前述算式，即可獲得該添加金屬之分散均勻度指標。 Preferably, the uniformity index (uniformity index, U%) of the added metal is less than or equal to 10%; wherein, the uniformity index of the added metal is measured by the composite ceramic target at different positions. The multiple sets of data of the added metal weight ratio are obtained by the following formula: (the maximum value of the added metal weight ratio in the multiple sets of data - the minimum value of the added metal weight ratio in the multiple sets of data) / 2 × The average value of the weight ratio of added metals in the multiple sets of data × 100%. Specifically, the maximum value (M _max ), the minimum value (M _min ) and the average value (M _avg ) of the added metal weight ratio in the multiple sets of data can be substituted into the following formula to obtain the dispersion uniformity index of the added metal .

Here, the dispersion uniformity index of the added metal represents the change rate of the weight ratio of the added metal at different positions of the composite ceramic target. Therefore, the lower the value of the dispersion uniformity index, the change in the weight ratio of the added metal. The smaller the ratio is, that is, the weight ratio of the added metal in different positions of the composite ceramic target is similar, which can be used to evaluate the overall uniform dispersion of the added metal in the composite ceramic target. For example, one point can be taken at the center of the target material and one point at every 90 degrees on the circumference of 10 cm from the center to obtain five positions, and then analyzed by Energy Dispersive Spectrometer (EDS) The weight percentage data of the added metal in the five positions, and then the maximum, minimum and average weight percentage of the added metal in the five groups of data measured are substituted into the aforementioned formula, and the dispersion uniformity index of the added metal can be obtained. .

Preferably, the maximum particle size of the added metal is less than or equal to 1 millimeter (mm). Specifically, the maximum particle size of the added metal refers to the maximum value of the particle size of the added metal measured in the metallographic phase of the composite ceramic target. More preferably, the maximum particle size of the added metal is less than or equal to 0.8 mm.

In an embodiment of the present invention, the maximum particle size of the added metal is greater than or equal to 0.1 mm and less than or equal to 1 mm; in another embodiment of the present invention, the maximum particle size of the added metal is greater than or equal to 1 mm. or equal to 0.1 mm and less than or equal to 0.8 mm.

In order to achieve the aforementioned object, the present invention further provides a method for making a composite ceramic target, which includes the following steps: Step (a): mixing a first metal oxide raw material, a second metal oxide raw material and an additive metal raw material to obtain a Obtaining a mixed raw material; step (b): subjecting the mixed raw material to cold isostatic pressing (CIP) to obtain a green body; and step (c): placing the green body in an oxygen atmosphere at a temperature greater than or equal to 1200 ° C and less than or equal to 1400 ° C for sintering to obtain the composite ceramic target; wherein, the number of crystal phases of the composite ceramic target is two phases, and the total weight of the mixed raw materials As a benchmark, the addition amount of the added metal raw material is greater than or equal to 0.3 wt% and less than or equal to 30 wt%, and the content of the second metal oxide raw material is greater than or equal to 0.5 wt% and less than or equal to 2 wt%; wherein , the first metal oxide raw material comprises tin dioxide raw material, titanium dioxide raw material, zinc monoxide raw material, indium trioxide raw material, molybdenum trioxide raw material, tungsten trioxide raw material, zirconium dioxide raw material or combination thereof, the second metal oxide raw material The oxide raw materials include copper monoxide raw materials, antimony trioxide raw materials, cobalt monoxide raw materials, manganese dioxide raw materials or combinations thereof, and the additive metal raw materials include palladium raw materials, platinum raw materials, ruthenium raw materials, gold raw materials, silver raw materials, and indium raw materials or a combination thereof.

By mainly controlling the pressing method of the mixed raw material, the added amount of the added metal raw material and the second metal oxide, the ambient atmosphere and the sintering temperature when the green body is sintered, and simultaneously controlling the crystal phase of the composite ceramic target Therefore, the composite ceramic target prepared by the method of this invention has the characteristics of high relative density, good dispersion uniformity of added metal and small particle size, which is conducive to further forming high-quality composite ceramic films.

Preferably, the average particle size of the added metal raw material is less than 80 micrometers (μm), the average particle size of the first metal oxide raw material is less than 1 μm, and the average particle size of the second metal oxide raw material is less than 1 μm. μm.

According to the present invention, before the first metal oxide raw material and the second metal oxide are mixed with the additive metal raw material, a refinement step can be performed to obtain a specific average particle size and dispersed and non-agglomerated refinement raw materials. For example, the refining step can be directly ball-milling and refining the raw material with zirconia balls; or firstly mixing the raw material, zirconia balls, water and dispersant for ball-milling, and then spray granulation to obtain the refined raw material , but not limited to this.

Preferably, the step (a) further comprises the following steps: step (a1): mixing the first metal oxide raw material and the second metal oxide raw material to obtain a metal oxide mixed raw material; step (a2): The metal oxide mixed raw material is subjected to a ball milling refinement step to make the average particle size less than 1 μm, and then a spray granulation step is performed to obtain a refined metal oxide mixed raw material; and step (a3): the refinement The metal oxide mixed raw material and the added metal raw material are ball-milled and mixed to obtain the mixed raw material.

In order to achieve the aforementioned objective, the present invention further provides a composite ceramic thin film, which is made from the aforementioned composite ceramic target through sputtering or vapor deposition.

Accordingly, the additive metal contained in the composite ceramic film has better dispersion uniformity and smaller particle size, and does not produce cracks and maintains good quality, which is beneficial to the application of subsequent gas detection.

In order to achieve the aforementioned objective, the present invention further provides a method for producing a composite ceramic film, which includes the following steps: sputtering or vapor-depositing the aforementioned composite ceramic target by means of radio frequency magnetron sputtering to obtain the composite ceramic film.

Accordingly, since the composite ceramic target provided by the present invention includes both added metal and metal oxide in a single target, it can be prepared by sputtering by radio frequency magnetron sputtering or by evaporation. Compared with the previous co-sputtering, the composite ceramic thin film needs to select targets of different materials and adjust the process parameters separately, which has the advantage of simplifying the process.

Preferably, the composite ceramic target is at room temperature, the pressure is greater than or equal to 3 mtorr (mtorr) and less than or equal to 20 mtorr, and the sputtering power is greater than or equal to 250 watts (W) and less than or equal to 350 W The composite ceramic thin film is formed by sputtering under the conditions.

Preferably, the composite ceramic target is evaporated at an evaporation rate of 1 ampere/sec to 5 ampere/sec to form the complex ceramic thin film.

In order to verify that the composite ceramic target provided by this creation has a two-phase crystalline phase, a relatively high relative density, and the additive metal contained in it has better dispersion uniformity and smaller particle size, several examples are listed below in detail. Describe the embodiment of this creation, those with ordinary knowledge in the art can easily understand the advantages and effects that this creation can achieve through the content of this specification, and make various modifications and changes without departing from the spirit of this creation, To implement or apply the content of this creation.

Example 1 to 5 : Composite ceramic target

Embodiments 1 to 5 are selected tin dioxide as the first metal oxide, selected copper monoxide as the second metal oxide and selected palladium as the additive metal, and weighed appropriate dioxide according to the composition ratio listed in table 1 below. Tin powder, copper monoxide powder and palladium powder. Next, place the tin dioxide powder and the copper monoxide powder in a solution containing zirconia balls, deionized water and a cationic dispersant for refining, and then spray granulation to obtain the refined tin dioxide and a cationic dispersant. The copper oxide mixed powders each have an average particle size of less than 1 μm.

Then, take the palladium powder with an average particle size of less than 80 μm and mix it with the above-mentioned refined tin dioxide and copper monoxide mixed powder with zirconia balls for ball milling to obtain mixed raw materials. The mixed raw materials are pressed into a green body, and then the green body is placed at a temperature of 1300° C. and sintered under an oxygen atmosphere to obtain the composite ceramic targets of Examples 1 to 5.

Comparative example 1 to 3 : Composite ceramic target

The production process of Comparative Examples 1 to 3 is similar to that of Examples 1 to 5, the difference is that Comparative Example 1 and Comparative Example 2 select the additive metal with lower content and higher content respectively; Except that the second metal oxide was added, the rest of the manufacturing process of Comparative Examples 1 to 3 was the same as that of Examples 1 to 5, and finally the composite ceramic targets of Comparative Examples 1 to 3 were prepared. The proportions of the components used in Comparative Examples 1 to 3 are also listed in Table 1 below.

Target crystal phase

The crystal phase of the target material is scanned by an X-ray diffraction analyzer (brand: Rigaku, model: Ultima IV) at a scanning speed of 2.4° per minute, and the diffraction angle is scanned from 2θ of 20° to 2θ of 80°. The composite ceramic targets of Examples 1 to 5 are analyzed, and the results are shown in FIG. 1 .

It can be seen from the results in FIG. 1 that several obvious diffraction peaks in the XRD analysis results of Examples 1 to 5 can be respectively corresponding to the XRD patterns of tin dioxide and the XRD patterns of palladium listed below. No other obvious diffraction peaks were observed in the XRD analysis results of 1 to 5. It can be seen that in the composite ceramic targets of Examples 1 to 5, there is no further reaction between palladium and tin dioxide, and they form independent crystalline phases. That is to say, the composite ceramic targets provided by this creation There is indeed a two-phase crystalline phase formed from both the additive metal and the first metal oxide, respectively.

Target relative density

The relative density of the target is measured by the Archimedes method. Specifically, the composite ceramic targets of Examples 1 to 5 and Comparative Examples 1 to 3 are respectively cut into 1 cm × 1 cm × by wire cutting. 1 cm of the sample to be tested, then immerse each sample to be tested in water, and measure the relative density of each sample to be tested under the condition that the water temperature is set to 25°C, the calculation method is: dry weight / (wet weight – water weight) × 100%. The relative densities of Examples 1 to 5 and Comparative Examples 1 to 3 are listed in Table 1 below.

It can be seen from the results in Table 1 that the relative densities measured by the composite ceramic targets of Examples 1 to 5 are all greater than or equal to 95%, showing good target quality; The composite ceramic target has no second metal oxide added during the production process, and the measured relative density is only 80%. It can be seen that the second metal oxide contained in the composite ceramic target can indeed increase the relative density to obtain better target quality, which is beneficial to the subsequent sputtering to form the composite ceramic thin film. Table 1: Composition and characteristic analysis of the composite ceramic targets of Examples 1 to 5 and Comparative Examples 1 to 3. first metal oxide add metal second metal oxide Relative density (%) Add metal dispersion uniformity index (%) Maximum particle size of added metal (mm) Example 1 SnO ₂ 0.3 wt% Pd 1 wt% CuO 95.1 10 0.8 Example 2 SnO ₂ 5.0 wt% Pd 1 wt% CuO 95.4 7.5 0.6 Example 3 SnO ₂ 8.5 wt% Pd 1 wt% CuO 95.5 6.3 0.3 Example 4 SnO ₂ 12 wt% Pd 1 wt% CuO 96 6.2 0.2 Example 5 SnO ₂ 30 wt% Pd 1 wt% CuO 95.6 8.6 0.8 Comparative Example 1 SnO ₂ 0.03 wt% Pd 1 wt% CuO 95.8 15.2 1.1 Comparative Example 2 SnO ₂ 35 wt% Pd 1 wt% CuO 95.7 13.2 1.2 Comparative Example 3 SnO ₂ 12 wt% Pd -- 80 6.1 0.3

Test example 1 : Dispersion uniformity index and particle size of added metal

In this test example, the composite ceramic targets of Examples 1 to 5 and Comparative Examples 1 to 3 were selected, and the metallographic images of each group of targets were obtained by scanning electron microscope (brand: HITACHI; model: S-3400N). , and then evaluate the dispersion uniformity index and particle size of the added metal in the target material in the following manner.

(1) Dispersion uniformity index

For the composite ceramic targets of Examples 1 to 5 and Comparative Examples 1 to 3, take a point at the center of the target (at A) and every 90 degrees on the circumference of 10 cm from the center (at B to E) , a total of five metallographic images at five positions were obtained, and then an elemental analyzer (brand HORIBA; model 7021-H) was used to analyze the weight ratio of the added metal in each of the five metallographic images, and five sets of data of the added metal weight ratio were obtained. , and according to this, the maximum value (M _max ), the minimum value (M _min ) and the average value (M _avg ) of the metal weight ratio in the five sets of data can be obtained, and then the aforementioned values can be substituted into the following formula, and the implementation can be obtained. Dispersion uniformity index of the added metal in the composite ceramic targets of Examples 1 to 5 and Comparative Examples 1 to 3. Among them, the lower the numerical value of the index of dispersion uniformity, the better the dispersion uniformity is represented, and the results are listed in Table 1 above.

Taking the composite ceramic target of Example 4 as an example, five sets of data on the weight ratio of added metals were obtained at five different positions (A to E) by a scanning electron microscope and an elemental analyzer, A to E The data are respectively 10.91%, 11.15%, 11.63%, 12.33% and 11.47% in sequence, from which it can be obtained that the M _max of the composite ceramic target of Example 4 is 12.33%, the M _min is 10.91% and the M _avg is 11.49%, and then substituted into the above formula, the dispersion uniformity index of the added metal in the composite ceramic target of Example 4 can be obtained to be about 6.2%; then take the composite ceramic target of Comparative Example 2 as an example, the same as the above. In this way, five groups of data of the weight proportion of the added metal can be obtained from A to E, which are 30.14%, 31.21%, 35.53%, 39.26% and 36.34%, respectively. From this, the composite ceramic target of Comparative Example 2 can be obtained. M _max is 39.26%, M _min is 30.14% and M _avg is 34.49%, and then substituting the above formula into the composite ceramic target of Comparative Example 2, the dispersion uniformity index of the added metal is about 13.2%.

As can be seen from the results in Table 1, in the composite ceramic targets of Examples 1 to 5, since the content of the added metal in the composite ceramic target is controlled within a specific range of 0.3 wt % to 30 wt %, the added The indexes of metal dispersion uniformity are all less than or equal to 10%, which means that the added metals are well dispersed in the composite ceramic targets of Examples 1 to 5; on the other hand, in the composite ceramic targets of Comparative Example 1 and Comparative Example 2, due to The content of the added metal is too low or too high and is not within the scope defined by this work, so that the dispersion uniformity index of the added metal is all greater than 10%. The problem of uneven dispersion.

(2) particle size

The composite ceramic targets of Examples 1 to 5 and Comparative Examples 1 to 3 also obtained the metallographic phase by SEM, and then measured the particle size of the added metal in the metallographic phase. The maximum particle sizes of the added metals measured in Examples 1 to 5 and Comparative Examples 1 to 3 are listed in Table 1 above; in addition, the metallographic phases of the composite ceramic targets of Example 4 and Comparative Example 2 are shown in Figures 2A and 2A. Figure 2B is used to illustrate the difference between the two.

From the results in Table 1, it can be seen that in the composite ceramic targets of Examples 1 to 5, since the content of the added metal is controlled within a specific range (0.3 wt% to 30 wt%), the maximum value of the added metal measured is The particle size is less than 1 mm, which means that the added metal will not agglomerate and has better dispersibility. In contrast, the results of the composite ceramic targets of Comparative Example 1 and Comparative Example 2 are not controlled because the content of the added metal is within a specific range. Therefore, the maximum particle size of the added metal is greater than 1 mm, that is, the added metal has the phenomenon of agglomeration and uneven dispersion.

In addition, it can be clearly observed from the results in FIGS. 2A and 2B that the additive metal (white part) shown in FIG. 2A obviously has a smaller particle size and is uniformly dispersed in the metallographic phase; while the additive metal presented in FIG. 2B The particle size is obviously larger and there is agglomeration and uneven dispersion.

From the above-mentioned experimental results of the dispersion uniformity index of the added metal and the particle size, it can be seen that the composite ceramic target of this creation does have the advantages of better dispersion uniformity of the added metal and smaller particle size, which is beneficial to improve the subsequent formation. film quality.

Test example 2 : Composite ceramic film quality

In this test example, the composite ceramic film formed by sputtering with the composite ceramic target of Example 2 is compared with the composite ceramic film formed by co-sputtering with a palladium target and a tin dioxide target respectively. Specifically, the composite ceramic target material of Example 2 adopts the method of radio frequency magnetron sputtering, at room temperature and under the pressure of 8 mtorr, the sputtering power is 300 W, and the ratio of oxygen to argon is five points. One of the following conditions forms a composite ceramic film with a film thickness of 150 nanometers (nm); and the co-sputtering condition is that the palladium target is DC magnetron sputtering with a sputtering power of 50 W, and a tin dioxide target is used. The material was sputtered by radio frequency magnetron sputtering with a sputtering power of 270 W, and sputtered together to form a composite ceramic film. Subsequently, both the composite ceramic film formed by the composite ceramic target of Example 2 and the composite ceramic film formed by co-sputtering were photographed with SEM to evaluate the quality of the films. The results are shown in Fig. 3A and Fig. 3A respectively. 3B is shown.

At the same time, it can be observed from the results of FIGS. 3A and 3B that the composite ceramic film of FIG. 3B has obvious cracks in many places, that is, there is a problem of cracking; while the composite ceramic film of FIG. 3A has no cracks. Accordingly, it can be seen from the comparison results of FIG. 3A and FIG. 3B that, compared with the composite ceramic thin film formed by co-sputtering, the composite ceramic thin film formed by sputtering with the composite ceramic target of the present invention will not crack. The problem is that the formed composite ceramic film does have better quality.

To sum up, by controlling the number of crystal phases of the composite ceramic target and the content of the second metal oxide and the additive metal in a specific range, the present invention can make the composite ceramic target have a higher relative density and The addition of metal in the target has better dispersion uniformity and smaller particle size, which can improve the quality of the composite ceramic film formed subsequently, and simplify the process of the composite ceramic film, thus improving its application in gas sensors. value in related fields.

none.

1 is the X-ray diffraction (X-ray Diffraction, XRD) analysis results of the composite ceramic targets of Examples 1 to 5 and the XRD patterns of palladium and tin dioxide; 2A is a scanning electron microscope (Scanning Electron Microscope, SEM) image of the composite ceramic target of Example 4; 2B is a SEM image of the composite ceramic target of Comparative Example 2; 3A is a SEM image of a composite ceramic film formed by sputtering of the composite ceramic target of Example 2; 3B is a SEM image of a composite ceramic thin film formed by co-sputtering.

none.

Claims (10)

A composite ceramic target, comprising a first metal oxide, a second metal oxide and an additive metal, the number of crystal phases of the composite ceramic target is two phases, and the total weight of the composite ceramic target is As a benchmark, the content of the added metal is greater than or equal to 0.3 weight percent and less than or equal to 30 weight percent, and the content of the second metal oxide is greater than or equal to 0.5 weight percent and less than or equal to 2 weight percent; One metal oxide is tin dioxide, the second metal oxide is copper monoxide, and the additive metal is handle. The composite ceramic target according to claim 1, wherein the relative density of the composite ceramic target is greater than or equal to 60%. The composite ceramic target according to claim 1, wherein the relative density of the composite ceramic target is greater than or equal to 95%. The composite ceramic target according to any one of claims 1 to 3, wherein the index of the dispersion uniformity of the added metal in the composite composite ceramic target is less than or equal to 10%; wherein, the dispersion uniformity of the added metal is The index is obtained from the multiple sets of data of the added metal weight ratio measured at different positions of the composite ceramic target through the following formula: (the maximum value of the added metal weight ratio in the multiple sets of data - the multiple The minimum value of the weight proportion of the added metal in the group data)/2×the average value of the weight proportion of the added metal in the multiple groups of data×100%. The composite ceramic target according to any one of claims 1 to 3, wherein the maximum particle size of the additive metal is less than or equal to 1 mm. A method for preparing a composite ceramic target, comprising the following steps: step (a): mixing a first metal oxide raw material, a second metal oxide raw material and an additive metal raw material to obtain a mixed raw material; step (b) : cold equalizing the mixed raw material to obtain a green body; and Step (c): the green body is placed in an oxygen atmosphere and the temperature is greater than or equal to 1200°C and less than or equal to 1400°C and sintered to obtain the composite ceramic target; wherein, the crystallization of the composite ceramic target The number of phases is two phases, and based on the total weight of the mixed raw materials, the amount of the added metal raw material is greater than or equal to 0.3 weight percent and less than or equal to 30 weight percent, and the content of the second metal oxide raw material is More than or equal to 0.5 weight percent and less than or equal to 2 weight percent; wherein, the first metal oxide raw material is a tin dioxide raw material, the second metal oxide raw material is a copper monoxide raw material, and the added metal raw material is a raw material. The method according to claim 6, wherein the average particle size of the added metal raw material is less than 80 microns, the average particle size of the first metal oxide raw material is less than 1 micron, and the average particle size of the second metal oxide raw material is less than 1 micron. The diameter is less than 1 micron. The production method according to claim 6, wherein the step (a) further comprises the following steps: step (a1): mixing the first metal oxide raw material and the second metal oxide raw material to obtain a mixed metal oxide raw material; step (a2): pass the metal oxide mixed raw material through a ball milling refining step to make the average particle diameter less than 1 micron, and then obtain a refined metal oxide mixed raw material through a spray granulation step; and step ( a3): The refined metal oxide mixed raw material and the added metal raw material are ball-milled and mixed to obtain the mixed raw material. A composite ceramic thin film is produced by sputtering or evaporation from the composite ceramic target according to any one of claims 1 to 5. A method for preparing a composite ceramic thin film, comprising the following steps: sputtering or evaporating the composite ceramic target according to any one of claims 1 to 5 by means of radio frequency magnetron sputtering to obtain the composite ceramic thin film.

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