CN107740058A - The preparation method of metal/non-metal laminated film with orthogonal array structure - Google Patents

Abstract

The invention discloses a kind of preparation method of the metal/non-metal laminated film with orthogonal array structure, this method is to prepare metal/non-metal compound structure film by rf magnetron sputtering codeposition technique, by strictly controlling nonmetallic target/metallic target power ratio condition in technical process to realize a wide range of regulation and control to metal array size, volume ratio；This technical process is environment-friendly, it is simple and easy, need not be by template, to substrate without particular/special requirement, it is the metal/non-metal orthogonal array structure of available different shape, size and crystalline state at room temperature, all there is good application potential and prospect in fields such as optics, catalysis, precision resistance film, storage, display devices, new technical thought is provided for the industrial applications of the laminated film of orthogonal array structure.

Description

Preparation method of metal/nonmetal composite film with vertical array structure

technical field

The invention relates to a metal/nonmetal composite film with a vertical array structure and a preparation method thereof, belonging to the technical field of metal/nonmetal composite film preparation; the prepared material is used for optical devices, catalysis, precision resistance films, storage and display devices and other fields.

Background technique

Metal/nonmetal composite thin films with a vertical array structure are widely used in optical devices, catalysis, precision resistance films, storage, display devices and other fields, but their efficient preparation has always been a problem. Electron beam lithography, template-assisted electrodeposition, laser direct writing, and focused ion beam micromachining have all been used to try to prepare thin films with vertical array structures, but electron beam lithography, laser direct writing, and focused ion beam micromachining The method is time-consuming and labor-intensive, cannot be prepared in a large area, and its unusually high cost is unacceptable. From the perspective of cost, template-assisted electrodeposition, especially porous alumina template-assisted electrodeposition, is the most feasible. However, the pore size of the porous alumina template itself limits the feature size of the composite film. Usually, this method is suitable for the preparation of several The array structure of hundreds of nanometers to several microns, and the preparation process is cumbersome, and it is also impossible to achieve large-area preparation. Although some people have begun to explore the use of vapor deposition methods for preparation, due to the complexity of the ceramic-metal array structure, it is difficult to control the size and crystallinity of the nanowire array, and the ceramic array in the generally prepared ceramic-metal array structure All are amorphous, which greatly limits the wide application of ceramic-metal composite films. Therefore, there is an urgent need in the industry to obtain ceramic-metal array thin films quickly and conveniently, and to make the array size and crystallization state adjustable.

The Chinese patent document with the publication number CN105242334A discloses a multilayer cermet film with broad-spectrum ultrafast nonlinear optical response and its preparation method. The cermet film is prepared by physical vapor deposition, although it has an array structure , but the size of the prepared arrays is only about 1.5nm, and the obtained ceramic arrays are all amorphous structures, and crystalline ceramics cannot be obtained. At the same time, the sputtering power ratio of ceramic and metal targets is too high, ranging from 6 to 20. A high proportion of ceramic atoms will interfere with the atomic arrangement of the metal array, resulting in many defects in the metal array, which in turn affects the quality of the composite film.

Contents of the invention

The purpose of the present invention is to overcome the above-mentioned shortcoming of the prior art, provide a kind of preparation method of the metal/non-metal composite thin film with vertical array structure, this method is to prepare metal by radio frequency magnetron co-sputtering technology by strictly controlling process parameter /Non-metal composite structure film; compared with the traditional process that needs to be prepared by template, such as electrochemical deposition or chemical liquid deposition method, this process adopts environmentally friendly physical vapor deposition technology, does not need template, and has no special effect on the substrate Require. And at room temperature, by strictly controlling the deposition conditions, a metal/non-metal composite film with controllable size, controllable crystallinity, and vertical array structure can be obtained.

In order to achieve the above object, the present invention adopts the following technical solutions to achieve:

The preparation method of the metal/nonmetal composite thin film with vertical array structure comprises the following steps:

1) Perform ultrasonic cleaning and drying on the substrate, then clamp it on the sample tray and send it into the sputtering chamber;

2) Install the metal target and the non-metal target on the target position with an unbalanced magnetic field, and pump the sputtering chamber to a predetermined background vacuum;

3) Using high-purity argon as the working gas, at a predetermined temperature, by controlling the power ratio of the non-metallic target and the metal target to a range of 1.25:1 to 5:1, sputtering the metal target and the non-metallic target, so that the material atoms are deposited in the following On a sample plate rotating at a certain speed;

4) The sample plate is taken out after being cooled to room temperature with the furnace in the sputtering chamber, and a metal/non-metal composite film with a vertical array structure is obtained.

Preferably, the substrate is any one of P-type single crystal silicon, sapphire, conductive glass, PET, plexiglass or quartz sheet.

Preferably, the metal target material includes copper, silver, gold, platinum, ruthenium, iridium, rhodium or aluminum; the non-metallic target material includes oxide, nitride or carbide; the oxide is aluminum oxide, oxide zinc, silicon oxide, titanium oxide or tungsten oxide, the nitride is silicon nitride, aluminum nitride, titanium nitride or zirconium nitride, and the carbide is silicon carbide, titanium carbide, tungsten carbide or chromium carbide.

Preferably, in step 2), the background vacuum degree is 1×10 ^-5 ~ 3×10 ^-4 Pa.

Preferably, in step 3), the purity of the high-purity argon gas is 99.999%, the working pressure is 0.1-0.3 Pa, and the predetermined temperature for sputtering is 25-100°C.

Preferably, in step 3), in the sputtering process, both the metal target and the non-metallic target are sputtered by radio frequency power, wherein the sputtering power range of the metal target is 20-40W, and the sputtering power range of the non-metallic target is 45W ~130W.

Preferably, in step 3), in the sputtering process, the applied negative bias voltage is -80--100V, and the sputtering time is 60-120 min.

Preferably, in step 3), the rotation speed of the sample disc is 10 degrees/second.

Preferably, in step 4), the cooling of the sample is carried out under an argon atmosphere of 0.1-0.3 Pa.

Preferably, in the obtained composite film, the metal array is a nanocrystalline structure, and the non-metallic array is a nanocrystalline structure or an amorphous structure; the metal array and the non-metallic array are arranged alternately, the array size is 2-11nm, and the volume ratio of the metal array is 20% to 70%.

The metal/nonmetal composite thin film with a vertical array structure and the preparation method thereof of the present invention utilize magnetron co-sputtering technology to directly realize the orderly deposition of metal and nonmetal material atoms on the substrate, thereby obtaining the metal/nonmetal composite film with a vertical array structure. Metal/non-metal 3D structures.

Compared with the prior art, the present invention has the following advantages:

1. The present invention can realize the preparation of the array thin film by adopting a lower power ratio of non-metal and metal targets, which can reduce defects in the metal array and improve the quality of the composite thin film. The size and volume ratio of the metal array in the composite film with a vertical array structure obtained by the present invention can be adjusted in a wider range, the size of the metal array can be adjusted from 2nm to 11nm, and the volume ratio of the metal array can be adjusted from 20% to 70%; and the ceramic Arrays can be either nanocrystalline or amorphous;

2. The present invention has no special requirements on the substrate material, and commonly used substrate materials can be used as the substrate, and does not require templates, and can be prepared in large areas;

3. The environment-friendly physical vapor deposition technology adopted in the present invention can in-situ prepare metal/non-metal composite films with a vertical array structure. The equipment is easy to operate, high in efficiency, high in reliability, and low in cost. Strict control can realize the control of the details of the array, and has good application prospects in the fields of optical devices, catalysis, precision resistive films, and storage.

Description of drawings

Figure 1(a)-(c) are transmission electron micrographs and electron diffraction patterns of Al ₂ O ₃ /Cu composite films;

Figure 2(a)-(c) are transmission electron micrographs and electron diffraction patterns of Al ₂ O ₃ /Ag composite films;

Fig. 3 (a)-(c) is the transmission electron microscope photograph and electron diffraction pattern thereof of SiN/Cu composite film 1;

Fig. 4 (a)-(c) is the transmission electron microscope photograph and electron diffraction pattern thereof of SiN/Cu composite thin film 2;

Fig. 5 (a)-(c) is the transmission electron microscope photograph and electron diffraction pattern thereof of SiC/Cu composite film 1;

Fig. 6 (a)-(c) is the transmission electron microscope photograph and electron diffraction pattern thereof of SiC/Cu composite film 2;

Figure 7(a)-(c) are transmission electron micrographs and electron diffraction patterns of ZnO/Cu composite thin films.

detailed description

Below in conjunction with accompanying drawing and embodiment the technical content of the present invention is described in further detail, but present embodiment is not intended to limit the present invention, all adopt similar method of the present invention and similar variation thereof, all should be included in the protection scope of the present invention.

The preparation method of the metal/nonmetal composite thin film with vertical array structure of the present invention comprises the following steps:

1) Ultrasonic cleaning and drying of substrates made of P-type monocrystalline silicon, sapphire, conductive glass, PET, plexiglass or quartz wafers, then clamping them on the sample tray and sending them into the sputtering chamber ;

2) It will include metal targets made of copper, silver, gold, platinum, ruthenium, iridium, rhodium or aluminum and materials including oxides of aluminum oxide, zinc oxide, titanium oxide or tungsten oxide, including silicon nitride, aluminum nitride , titanium nitride, zirconium nitride, or carbide non-metallic targets including silicon carbide, titanium carbide, tungsten carbide or chromium carbide are installed on the target position with an unbalanced magnetic field, and the sputtering chamber is pumped to a predetermined position The background vacuum is 1×10 ^-5 ~ 3×10 ^-4 Pa;

3) Use high-purity argon with a purity of 99.999% as the working gas, and the working pressure is 0.1-0.3Pa; at a predetermined temperature of 25-100°C, the power ratio of the non-metallic target to the metal target ranges from 1.25:1 to 5 :1 Sputtering metal target and non-metallic target, metal target and non-metallic target are sputtered by radio frequency power supply, the sputtering power range of the metal target is 20-40W, and the sputtering power range of the non-metallic target is 45-130W, The negative bias voltage is -80~-100V, and the sputtering time is 90-120min; the material atoms are deposited on the sample disk rotating at a speed of 10 degrees/second;

4) The sample disc is cooled to room temperature in the sputtering chamber in an argon atmosphere of 0.1-0.3 Pa, and then taken out to obtain a metal/non-metal composite film with a vertical array structure.

Specific examples are given below to further illustrate the method of the present invention.

Example 1

Preparation of Al ₂ O ₃ /Cu vertical array composite thin film: select P-type single crystal silicon (resistivity is about 9-15Ω·cm, and there is an oxide layer with a thickness of 2±0.5nm on it) as the substrate, sequentially in Acetone, absolute ethanol, and deionized water were sonicated for 15 minutes, and dried in a nitrogen atmosphere. After drying, the substrate was clamped on the sample tray and sent into the sputtering chamber. Then install the copper target (purity 99.999%) and alumina target (purity 99.99%) respectively on the unbalanced magnetron target position, pump the background vacuum of the sputtering chamber to 2×10 ^-4 Pa and start coating operate. Introduce Ar (purity 99.999%) gas and keep the working pressure at 0.15Pa. Co-sputter the copper target and alumina target with radio frequency power supply. The power of alumina and copper is 120W and 40W respectively. The power ratio of ceramic and metal targets is The temperature is 3:1, the substrate temperature is 25°C, turn on the rotation switch of the sample disk, and the substrate is rotated at a speed of 10 degrees/second, and a negative bias voltage of -80V is applied during the sputtering process, and the sputtering time is 90min . The samples were cooled under an argon atmosphere of 0.1 Pa.

The volume ratio of the metal array of the resulting composite film is 50%, and the film thickness is 110nm; it can be seen from Figure ₁ (a) that the array formed by _Al2O3 and Cu interlaced arrangement has high verticality; it can be seen from Figure 1 (b) that the array size is About 3nm; Figure 1(c) shows that the Al ₂ O ₃ array is an amorphous structure, and the Cu array is a nanocrystalline structure.

Example 2

Preparation of Al ₂ O ₃ /Ag vertical array composite thin film: use conductive glass as the substrate, sonicate in acetone, absolute ethanol, and deionized water for 15 minutes, and dry in a nitrogen atmosphere. After being clamped on the sample tray, it is sent into the sputtering chamber. Then install the silver target (purity 99.999%) and alumina target (purity 99.99%) respectively on the unbalanced magnetron target position, pump the background vacuum of the sputtering chamber to 1×10 ^-4 Pa and start coating operate. Introduce Ar (purity 99.999%) gas and keep the working pressure at 0.10Pa, use RF power supply to co-sputter the silver target and alumina target, the power of alumina and silver is 120W and 30W respectively, the power ratio of ceramic and metal targets The temperature is 4:1, the substrate temperature is 100°C, turn on the rotation switch of the sample plate, and the substrate is rotated at a speed of 10 degrees/second, and a negative bias voltage of -100V is applied during the sputtering process, and the sputtering time is 60min . The samples were cooled under an argon atmosphere of 0.3 Pa.

The volume ratio of the metal array of the resulting composite film is 45%, and the film thickness is 60nm; it can be seen from Figure ₂ (a) that the array formed by _Al2O3 and Ag interlaced arrangement has high verticality; it can be seen from Figure 2 (b) that the array size is About 4nm; Figure 2(c) shows that the Al ₂ O ₃ array is an amorphous structure, and the Ag array is a nanocrystalline structure.

Example 3

Preparation of SiN/Cu vertical array composite thin film: choose quartz plate as the substrate, ultrasonic in acetone, absolute ethanol, and deionized water for 15 minutes, and dry in nitrogen atmosphere. After drying, the substrate is clamped in the test After being placed on the sample tray, it is sent into the sputtering chamber. Then install the copper target (purity 99.999%) and silicon nitride target (purity 99.99%) respectively on the unbalanced magnetron target position, and start after the background vacuum of the sputtering chamber is pumped to 1×10 ^-5 Pa Coating operation. Introduce Ar (purity 99.999%) gas and keep the working pressure at 0.10Pa. Co-sputter the copper target and silicon nitride target with RF power. The power of silicon nitride and copper is 100W and 20W respectively. Ceramic and metal targets The power ratio is 5:1, the substrate temperature is 60°C, turn on the rotation switch of the sample plate, and the substrate is rotated at a speed of 10 degrees/second, and a negative bias voltage of -80V is applied during the sputtering process, and the sputtering time is for 90min. The samples were cooled under an argon atmosphere of 0.2 Pa.

The metal array volume ratio of the obtained composite film is 70%, and the film thickness is 52nm; it can be seen from Figure 3 (a) that the array formed by the staggered arrangement of SiN and Cu has high verticality; it can be seen from Figure 3 (b) that the array size is 3-5nm Left and right; from Figure 3 (c) it can be seen that the SiN array is an amorphous structure, and the Cu array is a nanocrystalline structure.

Example 4

Preparation of SiN/Cu vertical array composite thin film: choose PET as the substrate, sonicate in acetone, absolute ethanol, and deionized water for 15 minutes, and dry in a nitrogen atmosphere. After drying, the substrate is clamped on the sample After being placed on the tray, it is sent into the sputtering chamber. Then install the copper target (purity 99.999%) and silicon nitride target (purity 99.99%) respectively on the unbalanced magnetron target position, and start after the background vacuum of the sputtering chamber is pumped to 8×10 ^-5 Pa Coating operation. Introduce Ar (purity 99.999%) gas and keep the working pressure at 0.15Pa. Co-sputter the copper target and silicon nitride target with RF power. The power of silicon nitride and copper is 130W and 40W respectively. Ceramic and metal targets The power ratio is 3.25:1, and the substrate temperature is 40°C. Turn on the rotation switch of the sample plate to make the substrate rotate at a speed of 10 degrees/second. During the sputtering process, a negative bias of -80V is applied, and the sputtering time is for 90min. The samples were cooled under an argon atmosphere of 0.2 Pa.

The metal array volume ratio of the obtained composite film is 45%, and the film thickness is 168nm; it can be seen from Figure 4 (a) that the array formed by the staggered arrangement of SiN and Cu has high verticality; it can be seen from Figure 4 (b) that the array size is about 3nm; It can be seen from Figure 4(c) that the SiN array is an amorphous structure, and the Cu array is a nanocrystalline structure.

Example 5

Preparation of SiC/Cu vertical array composite thin film: select sapphire as the substrate, sonicate in acetone, absolute ethanol, and deionized water for 15 minutes, and dry in a nitrogen atmosphere. After drying, the substrate is clamped on the sample After being placed on the tray, it is sent into the sputtering chamber. Then install the copper target (purity 99.999%) and silicon carbide target (purity 99.99%) respectively on the unbalanced magnetron target position, pump the background vacuum of the sputtering chamber to 3×10 ^-4 Pa and start coating operate. Introduce Ar (purity 99.999%) gas and keep the working pressure at 0.3Pa. Co-sputter the copper target and silicon nitride target with RF power. The power of silicon carbide and copper is 85W and 20W respectively, and the power of ceramic and metal targets The ratio is 4.25:1, the substrate temperature is 60°C, turn on the rotation switch of the sample plate, and the substrate is rotated at a speed of 10 degrees/second, and a negative bias voltage of -90V is applied during the sputtering process, and the sputtering time is 120min.

The metal array volume ratio of the obtained composite film is 25%, and the film thickness is 74nm; it can be seen from Figure 5 (a) that the array formed by the staggered arrangement of SiC and Cu has high verticality; it can be seen from Figure 5 (b) that the array size is about 4nm; It can be seen from Figure 5(c) that the SiC array is an amorphous structure, and the Cu array is a nanocrystalline structure.

Example 6

Preparation of SiC/Cu vertical array composite thin film: select P-type silicon as the substrate, ultrasonically in acetone, absolute ethanol, and deionized water for 15 minutes, and dry in a nitrogen atmosphere. After drying, the substrate is clamped in After the sample tray is placed, it is sent into the sputtering chamber. Then install the copper target (purity 99.999%) and the silicon carbide target (purity 99.99%) respectively on the unbalanced magnetron target position, pump the background vacuum of the sputtering chamber to 2×10 ^-5 Pa and start coating operate. Introduce Ar (purity 99.999%) gas and keep the working pressure at 0.2Pa. Co-sputter the copper target and silicon nitride target with RF power. The power of silicon carbide and copper is 120W and 40W respectively, and the power of ceramic and metal targets The ratio is 3:1, the substrate temperature is 25°C, turn on the rotation switch of the sample disk, and the substrate is rotated at a speed of 10 degrees/second, and a negative bias voltage of -100V is applied during the sputtering process, and the sputtering time is 60min.

The metal array volume ratio of the obtained composite film is 58%, and the film thickness is 148nm; it can be seen from Figure 6(a) that the array formed by the staggered arrangement of SiC and Cu has high verticality; it can be seen from Figure 6(b) that the array size is 7-11nm Left and right; from Figure 6 (c) it can be seen that the SiC array is an amorphous structure, and the Cu array is a nanocrystalline structure.

Example 7

Preparation of ZnO/Cu vertical array composite thin film: use plexiglass as the substrate, ultrasonic in acetone, absolute ethanol, and deionized water for 15 min, and dry in a nitrogen atmosphere. After drying, the substrate is clamped in the test After being placed on the sample tray, it is sent into the sputtering chamber. Then install the copper target (purity 99.999%) and the zinc oxide target (purity 99.99%) respectively on the unbalanced magnetron target position, pump the background vacuum of the sputtering chamber to 1×10 ^-5 Pa and start coating operate. Introduce Ar (purity 99.999%) gas and keep the working pressure at 0.3Pa. Co-sputter the copper target and zinc oxide target with RF power. The power of zinc oxide and copper is 45W and 40W respectively. The power ratio of ceramic and metal targets is The temperature is 1.25:1, the substrate temperature is 100°C, the rotation switch of the sample plate is turned on, and the substrate is rotated at a speed of 10 degrees/second, and a negative bias voltage of -100V is applied during the sputtering process, and the sputtering time is 90min .

The metal array volume ratio of the resulting composite film is 20%, and the film thickness is 135nm; it can be seen from Figure 7 (a) that the array formed by the staggered arrangement of ZnO and Cu has high verticality; it can be seen from Figure 7 (b) that the array size is about 2nm; It can be seen from Fig. 7(c) that the ZnO array has a nanocrystalline structure, and the Cu array also has a nanocrystalline structure.

The metal target material used in the present invention is not limited to the above-mentioned copper and silver materials, and gold, platinum, ruthenium, iridium, rhodium or aluminum metal target materials can also be used; the non-metallic target material used in the present invention is not limited to the above materials, and oxidation Silicon, titanium oxide, tungsten oxide, aluminum nitride, titanium nitride, zirconium nitride, titanium carbide, tungsten carbide or chromium carbide non-metallic targets.

The following table 1 shows the comparison between the metal/non-metal composite film with vertical array structure prepared by the method of the present invention and the cases in other open documents.

Table 1

Ceramic/Metal Power Ratio volume ratio of metal Metal Array Size Ceramic/Metal Structure comparative example 6～20 3%～50% 1~2nm Amorphous/Crystal Example 1 3 ~50% 3nm Amorphous/nanocrystalline Example 2 4 ~45% 4nm Amorphous/nanocrystalline Example 3 5 ~70% 3~5nm Amorphous/nanocrystalline Example 4 3.25 ~45% 3nm Amorphous/nanocrystalline Example 5 4.25 ~25% 4nm Amorphous/nanocrystalline Example 6 3 ~58% 7~11nm Amorphous/nanocrystalline Example 7 1.25 ~20% 2nm Nanocrystalline / Nanocrystalline

As can be seen from the above comparison, the metal array size of the metal/non-metal composite thin film with a vertical array structure obtained by the method of the present invention can be adjusted from 2nm to 11nm, and the volume ratio of the metal array can be adjusted from 20% to 70%. At the same time, the obtained non-metallic array can be both amorphous and nanocrystalline, which expands the existence form of metal/non-metal vertical array structure. The preparation of the array thin film can be realized only with a relatively low power ratio of the ceramic-metal target, which can reduce defects in the metal array and improve the quality of the composite thin film. The metal/nonmetal composite thin film with a vertical array structure obtained by the preparation process has good application prospects in the fields of optical devices, catalysis, precision resistance films, storage, display devices and the like.

It can be understood that although the present invention has been disclosed above with preferred embodiments, the above embodiments are not intended to limit the present invention. For anyone skilled in the art, without departing from the scope of the technical solution of the present invention, the technical content disclosed above can be used to make many possible changes and modifications to the technical solution of the present invention, or be modified to be equivalent to equivalent changes. Example. Therefore, any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention, which do not deviate from the technical solution of the present invention, still fall within the protection scope of the technical solution of the present invention.

Claims (10)

1. the preparation method of the metal/non-metal laminated film with orthogonal array structure, it is characterised in that including following step Suddenly：

1) substrate is cleaned by ultrasonic and drying process, then by its clamping on sample tray, and is sent into sputter chamber；

2) metal targets and nonmetallic target are arranged on the target position with unbalanced magnetic field, and sputter chamber is evacuated to predetermined Background vacuum；

3) using high-purity argon gas as working gas, at a predetermined temperature by controlling nonmetallic target and the metallic target power ratio range to be 1.25:1~5:1, splash-proofing sputtering metal target and nonmetallic target are deposited on material atom with the platter of certain speed rotation；

4) platter is taken out after cooling to room temperature with the furnace in sputter chamber, obtains metal/non-gold with orthogonal array structure Belong to laminated film.

2. the preparation method of the metal/non-metal laminated film according to claim 1 with orthogonal array structure, it is special Sign is that the substrate is any one in p type single crystal silicon, sapphire, electro-conductive glass, PET, lucite or quartz plate.

3. the preparation method of the metal/non-metal laminated film according to claim 1 with orthogonal array structure, it is special Sign is that the metallic target material includes copper, silver, gold, platinum, ruthenium, iridium, rhodium or aluminium；The nonmetallic target material include oxide, Nitride or carbide；The oxide is aluminum oxide, zinc oxide, silica, titanium oxide or tungsten oxide, and the nitride is nitrogen SiClx, aluminium nitride, titanium nitride or zirconium nitride, the carbide are carborundum, titanium carbide, tungsten carbide or chromium carbide.

4. the preparation method of the metal/non-metal laminated film according to claim 1 with orthogonal array structure, it is special Sign is, in step 2), background vacuum is 1 × 10^-5~3 × 10^-4Pa。

5. the preparation method of the metal/non-metal laminated film according to claim 1 with orthogonal array structure, it is special Sign is, in step 3), high-purity argon gas purity is 99.999%, and operating air pressure is 0.1~0.3Pa；The predetermined temperature of sputtering is 25~100 DEG C.

6. the preparation method of the metal/non-metal laminated film according to claim 1 with orthogonal array structure, it is special Sign is, in step 3), the sputter procedure, metallic target and nonmetallic target are sputtered using radio-frequency power supply, wherein metallic target Sputtering power scope is 20~40W, and the sputtering power scope of nonmetallic target is 45~130W.

7. the preparation method of the metal/non-metal laminated film according to claim 1 with orthogonal array structure, it is special Sign is, in step 3), the sputter procedure, added back bias voltage is -80~-100V, and sputtering time is 60~120min.

8. the preparation method of the metal/non-metal laminated film according to claim 1 with orthogonal array structure, it is special Sign is, in step 3), the rotational velocity of platter is 10 degrees seconds.

9. the preparation method of the metal/non-metal laminated film according to claim 1 with orthogonal array structure, it is special Sign is, in step 4), being cooled under 0.1~0.3Pa argon gas atmosphere for sample is carried out.

10. the preparation method of the metal/non-metal laminated film according to claim 1 with orthogonal array structure, its It is characterised by, in resulting laminated film, metal array is nanocrystalline structure, and nonmetallic array is nanocrystalline structure or amorphous Structure；Metal array and nonmetallic array are staggered, and array sizes are in 2~11nm, metal array volume ratio 20%~70%.