CN102560357B - Preparation method of boron nitride optical film - Google Patents
Preparation method of boron nitride optical film Download PDFInfo
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- CN102560357B CN102560357B CN 201210020466 CN201210020466A CN102560357B CN 102560357 B CN102560357 B CN 102560357B CN 201210020466 CN201210020466 CN 201210020466 CN 201210020466 A CN201210020466 A CN 201210020466A CN 102560357 B CN102560357 B CN 102560357B
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Abstract
The invention relates to a preparation method of a cubic boron nitride optical film. According to the invention, a cubic boron nitride film is prepared on a monocrystalline silicon (100) substrate through a radio frequency magnetron sputtering method. A small amount of Si is added in a sintered hexagonal BN target material, such that a small amount of microcrystalline silicon or amorphous siliconis formed in the cubic boron nitride film or between the cubic boron nitride film and the substrate. Therefore, performance differences between the cubic boron nitride film and the monocrystalline silicon substrate are reduced. Further, busting stripping of the film and the substrate can be avoided, and the compactness and the bonding force between the film and the substrate are improved. With reasonable parameter control, a uniform and relatively thick cubic boron nitride optical film can be prepared.
Description
Technical field
The present invention relates to a kind of preparation method of optical thin film, specifically a kind of preparation method of cubic boron nitride optical thin film.
Background technology
Cubic boron nitride has the hardness of superelevation, is only second to diamond, yet it has the unrivaled high temperature use properties of diamond again, avoids high temperature oxidation or reacts with other material.Except superpower hardness and chemical stability; cubic boron nitride is transparent in infrared and visible spectrum range; has extremely wide forbidden band; be aided with inferior adamantine hardness and high thermal conductivity; its optical application prospect is also very tempting; very likely substitute diamond and use as the optical window material, perhaps the protection plated film as optical element uses.
Yet, because synthesizing cubic boron nitride need carry out under High Temperature High Pressure usually, preparation cost is very high, and also is difficult to prepare large-scale cubic boron nitride components and parts, so people will be at optical element surface plating cubic boron nitride film as main research direction.But when the cubic boron nitride film for preparing usually generally has very high residual stress, particularly thickness to surpass about 200nm, be easy to peel off from substrate.And in order to make film obtain actual application, exactly need the thickness of film at least will be in about μ m rank.
Therefore, the practical application of cubic boron nitride optical thin film has been subjected to serious obstruction.How can control preparation technology, to satisfy service requirements thereby obtain a kind of thickness, and with matrix bond densification, the cubic boron nitride optical thin film that is not easy to peel off, be that people are devoted to the problem that solves always.
Summary of the invention
Purpose of the present invention namely is to provide a kind of preparation technology that can improve cubic boron nitride optical thin film and matrix bond compactness and film thickness and then raising cubic boron nitride optical thin film over-all properties.
For achieving the above object, the technical solution adopted in the present invention may further comprise the steps:
At first, select for use silicon single crystal as body material, in ultrasonic wave, clean the back with acetone and dry up standby with argon gas.
Subsequently, matrix is put on the vacuum chamber sample table of rf magnetron sputtering, and sintering hexagonal BN target is placed target position, be added with the Si that accounts for atom total amount 3-7% in the described sintering hexagonal BN target.
Subsequently vacuum tightness in the vacuum chamber is extracted into≤5 * 10
-4Pa, feeding flow simultaneously is the pure Ar of 300-350sccm, when gas pressure in vacuum is 2-3Pa, pre-sputter 5-10min, the power of pre-sputter is 150-200W, substrate bias is 500-600V, substrate temperature is 430-470 ℃, with impurity and the activated surface atom activity of further removing matrix surface.
Begin to feed the N that flow is 8-12sccm subsequently
2And the flow that reduces Ar is that 28-32sccm, gas pressure in vacuum are that the negative bias of 0.9-1.1Pa, body material is 150-200V, the temperature of keeping body material is 430-470 ℃, remove the baffle plate of BN target, carry out sputter with 300-350W power, sputtering time is 3h at least, satisfies the cubic boron nitride optical thin film of thickness requirement with formation.
Keep the inert atmosphere of Ar subsequently, under 800-900 ℃ of condition film is implemented insulation and handle, the treatment time is 1-1.5h.
Advantage of the present invention is: add certain Si in sintering hexagonal BN target, thereby can be in cubic boron nitride film or between cubic boron nitride film and the matrix, form a spot of crystallite or non-crystalline silicon, thereby reduce the difference of cubic boron nitride film and single crystal silicon substrate material, and then avoided the explosion of film and matrix to peel off, improved compactness and the bonding force of film and matrix; By reasonable parameter control, prepare even and thicker cubic boron nitride optical thin film.
Embodiment
Below, the present invention is described in detail by specific embodiment.
Embodiment 1.
At first, select for use silicon single crystal (100) as body material, with acetone in ultrasonic wave, clean dry up with argon gas behind the 10min standby.
Subsequently, matrix is put on the vacuum chamber sample table of rf magnetron sputtering, and sintering hexagonal BN target is placed target position, be added with the Si that accounts for atom total amount 3% in the described sintering hexagonal BN target.
Subsequently vacuum tightness in the vacuum chamber is extracted into≤5 * 10
-4Pa, feeding flow simultaneously is the pure Ar of 300sccm, when gas pressure in vacuum is 2Pa, pre-sputter 5min, the power of pre-sputter is 150W, and substrate bias is 500V, and substrate temperature is 430 ℃, with impurity and the activated surface atom activity of further removing matrix surface.
Begin to feed the N that flow is 8sccm subsequently
2, and the flow that reduces Ar is that 32sccm, gas pressure in vacuum are that the negative bias of 0.9Pa, body material is 150V, the temperature of keeping body material is 430 ℃, remove the baffle plate of BN target, carry out sputter with 300W power, sputtering time 3h satisfies the cubic boron nitride optical thin film of thickness requirement with formation.
Keep the inert atmosphere of Ar subsequently, under 800 ℃ of conditions film is implemented insulation and handle, the treatment time is 1h.
After testing, main absorption peak in the film is cubic boron nitride and do not find tangible hexagonal boron nitride absorption peak, film hardness is about 35GPa, shown that also it mainly is cubic boron nitride, coat-thickness is about 200nm, and phenomenon only appears peeling off on a small quantity in the long-time back coatingsurface of placing under atmospheric environment.
Embodiment 2.
Identical with embodiment 1, select for use silicon single crystal (100) as body material, with acetone in ultrasonic wave, clean dry up with argon gas behind the 10min standby.
Subsequently, matrix is put on the vacuum chamber sample table of rf magnetron sputtering, and sintering hexagonal BN target is placed target position, be added with the Si that accounts for atom total amount 5% in the described sintering hexagonal BN target.
Subsequently vacuum tightness in the vacuum chamber is extracted into≤5 * 10
-4Pa, feeding flow simultaneously is the pure Ar of 330sccm, when gas pressure in vacuum is 2.5Pa, pre-sputter 8min, the power of pre-sputter is 170W, substrate bias is 550V, substrate temperature is 450 ℃, with impurity and the activated surface atom activity of further removing matrix surface.
Begin to feed the N that flow is 10sccm subsequently
2, and the flow that reduces Ar is that 30sccm, gas pressure in vacuum are that the negative bias of 1Pa, body material is 180V, the temperature of keeping body material is 450 ℃, remove the baffle plate of BN target, carry out sputter with 330W power, sputtering time 5h satisfies the cubic boron nitride optical thin film of thickness requirement with formation.
Keep the inert atmosphere of Ar subsequently, under 850 ℃ of conditions film is implemented insulation and handle, the treatment time is 1.3h.
After testing, main absorption peak in the film is cubic boron nitride and do not find tangible hexagonal boron nitride absorption peak, film hardness is about 34GPa, shown that also it mainly is cubic boron nitride, coat-thickness is about 400nm, and phenomenon does not appear obviously peeling off in the long-time back coatingsurface of placing under atmospheric environment.
Embodiment 3.
Identical with embodiment 1, select for use silicon single crystal (100) as body material, with acetone in ultrasonic wave, clean dry up with argon gas behind the 10min standby.
Subsequently, matrix is put on the vacuum chamber sample table of rf magnetron sputtering, and sintering hexagonal BN target is placed target position, be added with the Si that accounts for atom total amount 7% in the described sintering hexagonal BN target.
Subsequently vacuum tightness in the vacuum chamber is extracted into≤5 * 10
-4Pa, feeding flow simultaneously is the pure Ar of 350sccm, when gas pressure in vacuum is 3Pa, pre-sputter 10min, the power of pre-sputter is 200W, and substrate bias is 600V, and substrate temperature is 470 ℃, with impurity and the activated surface atom activity of further removing matrix surface.
Begin to feed the N that flow is 12sccm subsequently
2, and the flow that reduces Ar is that 28sccm, gas pressure in vacuum are that the negative bias of 1.1Pa, body material is 200V, the temperature of keeping body material is 470 ℃, remove the baffle plate of BN target, carry out sputter with 350W power, sputtering time 10h satisfies the cubic boron nitride optical thin film of thickness requirement with formation.
Keep the inert atmosphere of Ar subsequently, under 900 ℃ of conditions film is implemented insulation and handle, the treatment time is 1.5h.
After testing, main absorption peak in the film is cubic boron nitride and do not find tangible hexagonal boron nitride absorption peak, film hardness is about 30GPa, shown that also it mainly is cubic boron nitride, coat-thickness is about 650nm, and phenomenon does not appear peeling off in the long-time back coatingsurface of placing under atmospheric environment.
By The above results as can be known, the addition of the Si among the embodiment 2 has been obtained the most excellent over-all properties, has also guaranteed the high rigidity of film when having improved the anti-stripping performance of film.
Claims (2)
1. the cubic boron nitride optical thin film of an excellent performance, its feature is being prepared by following steps:
Step 1) selects for use silicon single crystal as body material, cleans the back with acetone in ultrasonic wave and dries up standby with argon gas;
Step 2), matrix is put on the vacuum chamber sample table of rf magnetron sputtering, and sintering hexagonal BN target is placed target position, be added with the Si that accounts for atom total amount 5% in the described sintering hexagonal BN target;
Step 3), vacuum tightness in the vacuum chamber is extracted into≤5 * 10
-4Pa, feeding flow simultaneously is the pure Ar of 300-350sccm, when gas pressure in vacuum is 2-3Pa, pre-sputter 5-10min, the power of pre-sputter is 150-200W, substrate bias is 500-600V, substrate temperature is 430-470 ℃, with impurity and the activated surface atom activity of further removing matrix surface;
Step 4) begins to feed the N that flow is 8-12sccm
2And the flow that reduces Ar is that 28-32sccm, gas pressure in vacuum are that the negative bias of 0.9-1.1Pa, body material is 150-200V, the temperature of keeping body material is 430-470 ℃, remove the baffle plate of BN target, carry out sputter with 300-350W power, sputtering time is 3h at least, satisfies the cubic boron nitride optical thin film of thickness requirement with formation;
Step 5) is kept the inert atmosphere of Ar, under 800-900 ℃ of condition film is implemented insulation and handles, and the treatment time is 1-1.5h;
Described cubic boron nitride optical thin film has the hardness of 34GPa at least, and the thickness of described cubic boron nitride optical thin film surpasses 400nm.
2. the application of various element surfaces in optical field of the described optical thin film of claim 1.
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