CN102965666A - Flexible substrate nanometer diamond film and preparation method thereof - Google Patents
Flexible substrate nanometer diamond film and preparation method thereof Download PDFInfo
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- CN102965666A CN102965666A CN2012104899173A CN201210489917A CN102965666A CN 102965666 A CN102965666 A CN 102965666A CN 2012104899173 A CN2012104899173 A CN 2012104899173A CN 201210489917 A CN201210489917 A CN 201210489917A CN 102965666 A CN102965666 A CN 102965666A
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Abstract
The invention relates to a flexible substrate nanometer diamond film and a preparation method thereof. The flexible substrate nanometer diamond film comprises a metal flexible substrate layer, a Ni transition layer, a diamond film layer and a nanometer diamond film layer. According to the preparation method, Ni is used as the transition layer, and the diamond film and the nanometer diamond film are prepared by a microwave plasma chemical vapor deposition (MPCVD) method, so that the adhesive force is enhanced, and the adhesive force of the film base is further enhanced by regulating the following key processing steps: (1) carrying out hydrogen treatment on the Ni transition layer to enhance the binding force between the transition layer Ni and the substrate and etch redundant Ni; (2) depositing the diamond film at high methane concentration to improve the nucleation rate of the subsequent nanometer diamond film; (3) depositing the nanometer diamond film at low methane concentration with Ar gas introduced; and (4) insulating and annealing. The flexible substrate nanometer diamond film is low in surface roughness and smooth in surface, and can be used for substituting polishing powder, so that the shortage of the conventional polishing process is effectively overcome, and the application range is widened. The preparation method is simple and easy to realize, and has high controllability and generality.
Description
Technical field
The present invention relates to a kind of polishing abrasive substance, be specifically related to a kind of flexible substrate nano-diamond film and preparation method thereof.
Background technology
Diamond thin has excellent polishing performance, and nano-diamond film has more smooth surface and lower frictional coefficient, and frictional coefficient can less than 0.05, adopt the microhardness of nano indenter measurement up to 8000kg/mm
2, almost deserve to be called " never wornout ", thereby nano-diamond film obtains a wide range of applications in fields such as electronics, frictional wear, MEMS (micro electro mechanical system) (MEMS), an emission, optics and electrochemistry.In recent years, development along with optical technology, polishing for the precision optics glass surface requires more and more higher, and traditional glossing uses the polishing powder polishing, take polishing powder from rare earth as main, can be divided three classes: nano-scale rare earth polishing powder (1nm～100nm), submicron order polishing powder from rare earth (100nm～1 μ m) and micron order polishing powder from rare earth (1 μ m～100 μ m).The general multiplex micron order polishing powder from rare earth of polishing; Granularity is less than the submicron order polishing powder from rare earth of 1 μ m because in the application in liquid-crystal display and compact disk field and output improves year by year; The nano-scale rare earth polishing powder also comes out, but its market share is also very little at present, belongs to development.At present, the low-grade polishing powder that China produces is more, but in the polishing powder from rare earth production of top grade with compare abroad that still there is a big difference, can't meet the demands, the polishing powder that high-end product uses still needs dependence on import.If thereby at the nano-diamond film of polishing tool plated surface last layer good uniformity, then be used for the meticulous polishing of glass etc., will greatly improve present China to the dependence of the high-grade polishing powder of import, and can obtain better polishing effect.But use diamond thin and the bonding force between substrate of vapour deposition process preparation lower, this is the bottleneck that the restriction diamond thin is used always.
A kind of flexible substrate nano-diamond film that is made of metal flexible substrate layer, transition layer (being formed by titanium, aluminium, molybdenum successively sputtering sedimentation), grinding layer is disclosed among the patent documentation CN 102634793A, but the sticking power of the nano-diamond film of this product on its substrate still is difficult to satisfy the requirement that day by day improves on the industrial application, and its process for producing is also comparatively complicated.
Summary of the invention
The technical problem to be solved in the present invention provides the low wear-resistant flexible substrate nano-diamond film of a kind of high adhesive force, difficult drop-off and its surfaceness, and discloses its preparation method.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
Design a kind of flexible substrate nano-diamond film, comprise metal flexible substrate layer, transition layer, grinding layer, described transition layer is sputtering sedimentation and the Ni intermediate metal that forms on the polished surface of described metal flexible substrate layer; Described grinding layer comprises diamond film layer and nano-diamond film layer, described diamond film layer is to utilize the microwave plasma enhanced chemical Vapor deposition process to form in described Ni intermediate metal deposition under the high methane concentration of 3～4sccm, and described nano-diamond film layer is to utilize microwave plasma enhanced chemical gaseous phase depositing process also logical H under the low methane concentrations of 1.5～1.8sccm
2With form in described diamond film layer deposition under the condition of Ar.
The preparation method of described flexible substrate nano-diamond film may further comprise the steps:
(1) substrate layer is processed: after first the surface of metal flexible substrate layer being polished, ultrasonic cleaning 10～25min in acetone soln, again with washed with de-ionized water 5～10min, and then in concentration is 10% dilute sulphuric acid, soak 12～15h, use at last washed with de-ionized water;
(2) transition layer preparation: splash-proofing sputtering metal Ni on the polished surface of metal flexible substrate layer makes transition layer with the C-S magnetic control sputtering device, the sputtering sedimentation condition is: sputtering current 0.8～1A, 300～320 ℃ of sputter temperature, the sputtering sedimentation time is 15～20min, Ar airshed 35～40sccm;
(3) transition layer is processed: will be coated with sample behind the Ni transition layer with diadust acetone soln ultrasonic cleaning 10～15min of 2～6%wt%, carry out the hydrogen processing to put into MPCVD equipment behind deionized water ultrasonic cleaning 2～5min again, actual conditions is as follows: microwave power 1400～1500W, gas pressure intensity 6～6.5KPa, 800～850 ℃ of underlayer temperatures, hydrogen flowing quantity 95～100sccm, treatment time 30～35min;
(4) high methane concentration deposit diamond film layer: after the upper step, logical hydrogen finished, kept other condition constant, and passed into methane, flow is 3～4sccm, depositing time 60～90min, formation of deposits diamond thin on transition layer;
(5) low methane concentrations deposit nano-diamond film layer: behind the upper EOS, pass into again Ar gas, flow 40～45sccm, microwave power 800～850W, gas pressure intensity 11～13KPa, 600～650 ℃ of underlayer temperatures, methane flow 1.5～1.8sccm, H
2Flow 2～5sccm, depositing time 180～210min;
(6) insulation and annealing: close the methane air intake valve behind the upper EOS and the adjusting process parameter is as follows: microwave power 1400～1500W, gas pressure intensity 6～6.5KPa, 800～850 ℃ of underlayer temperatures, hydrogen flowing quantity 95～100sccm, keep with this understanding closing MPCVD equipment behind 10～12min, make sample nature slow cooling to room temperature.
Described metal flexible substrate layer is for being the Copper Foil of thickness 120～200 μ m.Utilize the characteristics of the characteristic of the unlimited solid solution of copper nickel and film forming core, growth to can further improve the sticking power of nano-diamond film on the flexible copper substrate.
The present invention has actively useful effect:
1. the present invention adopts Ni to do transition layer, use chemical gaseous phase depositing process (MPCVD) preparation diamond thin and nano-diamond film, improved the sticking power of grinding layer for the film base, and further improved the sticking power on the film base of diamond thin by the processing parameter of adjusting following critical process step: 1. the Ni transition layer is carried out hydrogen and process, strengthen the bonding force of transition layer Ni and substrate and etch away unnecessary Ni; 2. high methane concentration deposit diamond thin improves the subsequently nucleation rate of nano-diamond film; 3. low methane concentrations and pass into Ar gas condition deposit nano-diamond film; 4. be incubated and annealing process.
2. easy, the easy realization of the inventive method, have stronger can handling and versatility.
Product of the present invention be used for glassy product etc. meticulous polishing, enlarged the Application Areas of diamond thin, also can substitute in the meticulous polishing of present glass the dependence to the high-grade powder of import, can improve simultaneously the working accuracy of glass, the scrap rate of reduction product, reduce the cost of glass elaborated fabrication.
Description of drawings
Fig. 1 is the structural representation of flexible substrate nano-diamond film of the present invention;
Fig. 2 is the SEM collection of illustrative plates of the flexible substrate nano-diamond film for preparing of the present invention;
Fig. 3 is the XRD figure spectrum of the flexible substrate nano-diamond film for preparing of the present invention;
Fig. 4 is the Raman collection of illustrative plates of the flexible substrate nano-diamond film for preparing of the present invention;
Fig. 5 is the impression test figure as a result of the flexible substrate nano-diamond film for preparing of the present invention.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.Involved raw material and plant and instrument among each embodiment are commercially available if no special instructions; Related check, detection method if no special instructions, then are ordinary method.
The preparation method of 1 one kinds of flexible substrate nano-diamond films of embodiment:
(1) (10 * 10 * 0.2mm) carry out surface treatment to the substrate Copper Foil, and treatment process is: soak ultrasonic cleaning 10min → washed with de-ionized water 2min in 10h → acetone soln in the polishing → acetone soln in the dilute sulphuric acid of ultrasonic cleaning 10min → washed with de-ionized water 5min → 10%;
(2) preparation of transition layer: the preparation of Ni transition layer C-S magnetic control sputtering device, the sputtering sedimentation actual conditions is as follows: sputtering current 0.9A, 310 ℃ of sputter temperature, the sputtering sedimentation time is 18min, Ar airshed 38sccm, in the whole sputter procedure, specimen holder does not stop rotation so that even film layer;
(3) sample that step 2 is obtained diadust acetone soln ultrasonic cleaning 10min, put into MPCVD equipment behind the deionized water ultrasonic cleaning 2min and carry out the hydrogen processing, actual conditions is as follows: microwave power 1450W, gas pressure intensity 6.5KPa, 800 ℃ of underlayer temperatures, hydrogen flowing quantity 98sccm, treatment time 30min;
(4) behind the upper EOS, pass into methane, flow is 3.5sccm, depositing diamond film, depositing time 80min;
(5) behind the upper EOS, pass into Ar gas, the preparation nano-diamond film, concrete mode of deposition is as follows: microwave power 820W, gas pressure intensity 12KPa, 640 ℃ of underlayer temperatures, methane flow 1.6sccm, H
2Flow 3.5sccm, Ar airshed 42sccm, depositing time 200min;
(6) close the methane air intake valve behind the upper EOS, the adjusting process parameter is as follows: microwave power 1500W, and gas pressure intensity 6.5KPa, 840 ℃ of underlayer temperatures, hydrogen flowing quantity 95sccm kept 11 minutes with this understanding;
(7) closing device after the upper EOS, the taking-up sample had both got the described nano-diamond film of patent of the present invention after the annealing process of a slow cooling of sample experience, temperature were down to room temperature.
The structure of the flexible substrate nano-diamond film that this example is prepared as shown in Figure 1, C(Copper among Fig. 1) refer to body material-Copper Foil, TL (Transition Layer) refers to transition layer; DF(Diamond Film) refers to the diamond thin for preparing under the high methane concentration; NCDF (Nanocrystalline Diamond Film) refers to the nano-diamond film of plasma reinforced chemical vapour deposition.
And the product that makes carried out a series of check, detected test, its result is referring to Fig. 2 to Fig. 5:
As seen from Figure 2: under high power SEM, can find out that the crystal grain of diamond thin is tiny, smooth surface is smooth;
(220) characteristic peak shows that the diamond of preparation is nano-diamond film in the XRD figure of Fig. 3, and the grain-size of using " Scherrer " formula to calculate prepared nano-diamond film is 25nm;
The diffraction peak at 1140 places shows that the diamond thin of preparation is nano level in the Raman spectrum of Fig. 4;
By the impression test result of Fig. 5 flexible substrate nano-diamond film, can see that membrane is combined with substrate well, the impression crackle is even, and film does not almost have obscission.
Above embodiment is only in order to explanation, and unrestricted technical scheme of the present invention, although with reference to above-described embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that: still can make amendment or be equal to replacement the present invention, and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (7)
1. a flexible substrate nano-diamond film comprises flexible metal substrate layer, transition layer, grinding layer, it is characterized in that, described transition layer is sputtering sedimentation and the Ni intermediate metal that forms on the polished surface of described flexible metal substrate layer; Described grinding layer comprises micron diamond thin film layer and nano-diamond film layer, described micron diamond thin film layer is to utilize the microwave plasma enhanced chemical Vapor deposition process to form in described Ni intermediate metal deposition under the high methane concentration of 3～4sccm, and described nano-diamond film layer is to utilize microwave plasma enhanced chemical gaseous phase depositing process also logical H under the low methane concentrations of 1.5～1.8sccm
2With form in described diamond film layer deposition under the condition of Ar.
2. flexible substrate nano-diamond film according to claim 1 is characterized in that, described flexible metal substrate layer is the Copper Foil of thickness 120～200 μ m.
3. flexible substrate nano-diamond film according to claim 1, it is characterized in that, the sputtering sedimentation condition of described Ni intermediate metal on the polished surface of described flexible metal substrate layer is: sputtering current 0.8～1A, 300～320 ℃ of sputter temperature, the sputtering sedimentation time is 15～20min, Ar airshed 35～40sccm.
4. flexible substrate nano-diamond film according to claim 1, it is characterized in that, the mode of deposition of described micron diamond thin film layer is: microwave power 1400～1500W, gas pressure intensity 6～6.5KPa, 800～850 ℃ of underlayer temperatures, methane flow 3～4sccm, depositing time 60～90min.
5. flexible substrate nano-diamond film according to claim 1 is characterized in that, the mode of deposition of described nano-diamond film layer is: microwave power 800～850W, gas pressure intensity 11～13KPa, 600～650 ℃ of underlayer temperatures, methane flow 1.5～1.8sccm, H
2Flow 2～5sccm, Ar airshed 40～45sccm, depositing time 180～210min.
6. the preparation method of flexible substrate nano-diamond film claimed in claim 1 may further comprise the steps:
(1) substrate layer is processed: after first the surface of metal flexible substrate layer being polished, ultrasonic cleaning 10～25min in acetone soln, again with washed with de-ionized water 5～10min, and then in concentration is 10% dilute sulphuric acid, soak 12～15h, use at last washed with de-ionized water;
(2) transition layer preparation: splash-proofing sputtering metal Ni on the polished surface of metal flexible substrate layer makes transition layer with the CS-300 magnetic control sputtering device, the sputtering sedimentation condition is: sputtering current 0.8～1A, 300～320 ℃ of sputter temperature, the sputtering sedimentation time is 15～20min, Ar airshed 35～40sccm;
(3) transition layer is processed: will be coated with sample behind the Ni transition layer with diadust acetone soln ultrasonic cleaning 10～15min of 2～6wt%, carry out the hydrogen processing to put into MPCVD equipment behind deionized water ultrasonic cleaning 2～5min again, actual conditions is as follows: microwave power 1400～1500W, gas pressure intensity 6～6.5KPa, 800～850 ℃ of underlayer temperatures, hydrogen flowing quantity 95～100sccm, treatment time 30～35min;
(4) high methane concentration deposit micron diamond thin film layer: after the upper step, logical hydrogen finished, kept other condition constant, and passed into methane, flow is 3～4sccm, depositing time 60～90min, formation of deposits micron diamond film on transition layer;
(5) low methane concentrations deposit nano-diamond film layer: behind the upper EOS, pass into again Ar gas, flow 40～45sccm, microwave power 800～850W, gas pressure intensity 11～13KPa, 600～650 ℃ of underlayer temperatures, methane flow 1.5～1.8sccm, H
2Flow 2～5sccm, depositing time 180～210min;
(6) insulation and annealing: close the methane air intake valve behind the upper EOS and the adjusting process parameter is as follows: microwave power 1400～1500W, gas pressure intensity 6～6.5KPa, 800～850 ℃ of underlayer temperatures, hydrogen flowing quantity 95～100sccm, keep with this understanding closing MPCVD equipment behind 10～12min, make sample nature slow cooling to room temperature.
7. the preparation method of flexible substrate nano-diamond film according to claim 6 is characterized in that, described metal flexible substrate layer is for being the Copper Foil of thickness 120～200 μ m.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104498894A (en) * | 2014-12-04 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Preparation method of porous diamond film |
| CN104561925A (en) * | 2015-01-20 | 2015-04-29 | 太原理工大学 | Method for preparing self-supporting diamond film |
| CN107236935A (en) * | 2017-04-28 | 2017-10-10 | 同济大学 | A kind of method that CVD diamond coatings are deposited on composite polycrystal-diamond |
| CN108091859A (en) * | 2017-12-14 | 2018-05-29 | 成都新柯力化工科技有限公司 | A kind of lithium battery molybdenum oxide/diamond anode material and preparation method thereof |
| CN110670035A (en) * | 2019-10-11 | 2020-01-10 | 陕西科技大学 | Cu-based CVD diamond heat-sinking sheet and preparation method thereof |
| CN111321466A (en) * | 2020-03-25 | 2020-06-23 | 武汉大学 | Method for growing large-size single crystal diamond and composite substrate for growth |
| CN112647056A (en) * | 2020-12-01 | 2021-04-13 | 上海征世科技有限公司 | Diamond film based on nano particle modification and preparation method thereof |
| CN112808259A (en) * | 2021-01-27 | 2021-05-18 | 河南工程学院 | Preparation method and application of hybrid nano-diamond |
| CN114231953A (en) * | 2021-11-24 | 2022-03-25 | 江苏籽硕科技有限公司 | Method for preparing nano diamond film by microwave plasma chemical vapor deposition method |
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| US6562715B1 (en) * | 2000-08-09 | 2003-05-13 | Applied Materials, Inc. | Barrier layer structure for copper metallization and method of forming the structure |
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| US6562715B1 (en) * | 2000-08-09 | 2003-05-13 | Applied Materials, Inc. | Barrier layer structure for copper metallization and method of forming the structure |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104498894A (en) * | 2014-12-04 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Preparation method of porous diamond film |
| CN104561925A (en) * | 2015-01-20 | 2015-04-29 | 太原理工大学 | Method for preparing self-supporting diamond film |
| CN104561925B (en) * | 2015-01-20 | 2017-04-26 | 太原理工大学 | Method for preparing self-supporting diamond film |
| CN107236935A (en) * | 2017-04-28 | 2017-10-10 | 同济大学 | A kind of method that CVD diamond coatings are deposited on composite polycrystal-diamond |
| CN108091859A (en) * | 2017-12-14 | 2018-05-29 | 成都新柯力化工科技有限公司 | A kind of lithium battery molybdenum oxide/diamond anode material and preparation method thereof |
| CN108091859B (en) * | 2017-12-14 | 2020-09-08 | 成都新柯力化工科技有限公司 | Molybdenum oxide/diamond negative electrode composite material for lithium battery and preparation method thereof |
| CN110670035A (en) * | 2019-10-11 | 2020-01-10 | 陕西科技大学 | Cu-based CVD diamond heat-sinking sheet and preparation method thereof |
| CN111321466A (en) * | 2020-03-25 | 2020-06-23 | 武汉大学 | Method for growing large-size single crystal diamond and composite substrate for growth |
| CN112647056A (en) * | 2020-12-01 | 2021-04-13 | 上海征世科技有限公司 | Diamond film based on nano particle modification and preparation method thereof |
| CN112808259A (en) * | 2021-01-27 | 2021-05-18 | 河南工程学院 | Preparation method and application of hybrid nano-diamond |
| CN112808259B (en) * | 2021-01-27 | 2022-09-16 | 河南工程学院 | Preparation method and application of hybrid nano-diamond |
| CN114231953A (en) * | 2021-11-24 | 2022-03-25 | 江苏籽硕科技有限公司 | Method for preparing nano diamond film by microwave plasma chemical vapor deposition method |
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