CN101935837A - Copper-based mosaic structure interface diamond coating and preparation method and application thereof - Google Patents
Copper-based mosaic structure interface diamond coating and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a copper-based mosaic structure interface diamond coating and a preparation method and application thereof. The coating consists of a copper-diamond composite coarse sanding plating layer, a copper reinforcing layer, a copper-diamond composite thin sanding layer and a CVD diamond epitaxial growth layer from the bottom to the top. The preparation method comprises the following steps of: 1, depositing the copper-diamond composite coarse sanding plating layer, the copper reinforcing layer and the copper-diamond composite thin sanding layer on a copper matrix in turn to obtain a workpiece deposited with the copper-diamond composite plating layer; and 2, performing homogeneous epitaxial growth on the diamond exposed on the surface of the workpiece deposited with the copper-diamond composite plating layer in a CVD diamond deposition system to obtain the continuous diamond coating. The copper-based mosaic structure interface diamond coating has the advantages of high purity, few impurities, low thermal stress and firm combination with the matrix, and is an ideal choice of a microelectronic heat sink material.
Description
Technical field
The invention belongs to the heat sink technical field of diamond film, particularly a kind of copper base pattern structure interface diamond coatings and its production and application.
Background technology
Pattern structure interface diamond coatings is meant that diamond partly gos deep into matrix inside, and matrix and diamond coatings are engaged on the interface, can greatly improve the bonding force of diamond film and matrix.
Along with the microelectronics high speed development, semiconductor integrated circuit package density is more and more higher.Superpower unicircuit, light emitting semiconductor device, diode laser matrix and microwave device have often limited the lifting of its power level because of heat dissipation problem.Existing electronics heat sink material, as Cu/Invar/Cu (CIC), Cu/Mo/Cu (CMC), inlaid materials such as Ni/Mo/Ni, though its thermal conductivity and thermal expansivity can be adjusted thermal conductivity and thermal expansivity according to inlaying combination thickness, whole structure is that thermal conductivity is reduced significantly, is difficult to satisfy the radiating requirements of following high-power component, press for to develop and have high heat conductance, and the novel microelectronic packaged material that is complementary of thermal expansivity and semiconductor material.
The research of novel electron packaged material has at present become the focus that various countries fall over each other to research and develop with preparation.Diamond is the highest material of thermal conductivity in the known material, and thermal conductivity is 2200W/m.K under the normal temperature, and thermal expansivity is about (0.86 ± 0.1) * 10
-6K
-1, and diamond is an isolator under the room temperature, is the ideal heat sink material.But pure diamond is difficult to forming process, and cost is very high, and pure diamond is heat sink to be difficult in the industry member widespread use.Copper is the metallic substance (thermal conductivity 383W/m.K) with higher heat-conductivity, and forming process is convenient, if can be on copper the depositing diamond film, utilize the high thermal conductivity of diamond film from microelectronic device, heat to be transferred on the copper radiator, then heat is dispersed in the media such as air, copper can be processed into the shape of various increase area of dissipations, is that a kind of desirable combination is heat sink.Yet copper and diamond chemical compatibility are very poor, and copper and adamantine wetting angle reach 140 °, and copper and adamantine thermal expansivity differ 18 times.Directly depositing diamond film film/basic bonding force is very low on copper, directly comes off from matrix mostly.Pre-deposition carbide forming element on the copper matrix (as Cr, W, Mo, Ti etc.) though transition layer can improve diamond film/basic bonding force by a relatively large margin, but after increasing transition layer, the interface resistance between diamond film and the copper increases considerably, and its overall thermal conductivity improves and be not obvious.
Summary of the invention
In order to overcome the shortcoming and defect that prior art exists, primary and foremost purpose of the present invention is to provide a kind of copper base pattern structure interface diamond coatings.
Another purpose of the present invention is to provide the preparation method of a kind of above-mentioned copper base pattern structure interface diamond coatings; The Cu-diamond composite deposite of this method high diamond content of galvanic deposit on the copper matrix deposits continuous diamond thin with CVD (abbreviation of Chemical Vapor Deposition, chemical vapour deposition) epitaxial growth method on composite deposite.The Cu-diamond composite deposite has reduced the interfacial dilation coefficient, and diffusion is integrated mutually with the Cu matrix in the CVD process, forms pattern structure interface diamond coatings.
A further object of the present invention is to provide the application of above-mentioned copper base pattern structure interface diamond coatings.
Purpose of the present invention is achieved through the following technical solutions: a kind of copper base pattern structure interface diamond coatings, described copper base pattern structure interface diamond coatings thick go up that sand coating, copper back-up coat, copper-diamond are compound carefully to be gone up layer of sand and form at CVD diamond epitaxially grown layer by copper-diamond is compound from top to bottom; Contain trace Cr in the described copper back-up coat.
The preparation method of above-mentioned a kind of copper base pattern structure interface diamond coatings, may further comprise the steps: the first step, deposit successively on the copper matrix copper-diamond compound thick on sand coating, copper back-up coat and copper-diamond compound thin on layer of sand, obtain depositing the workpiece of copper-diamond composite deposite; In second step, in CVD diamond deposition system, isoepitaxial growth goes out the successive diamond coatings on the diamond that the workpiece surface that deposits the copper-diamond composite deposite is appeared.
The described the first step specifically comprises following operation steps:
(1) sand copper facing plating bath in the preparation: the described sand copper facing plating bath of going up comprises following component by mass volume ratio: ventilation breather (Cu
2(OH)
2CO
3) 55～65g/L, ethylenediamine tetraacetic acid (EDTA) (EDTA) 10～20g/L, citric acid (C
6H
8O
7) 250～290g/L, Seignette salt (C
4O
6H
2KNa) 40～50g/L, bicarbonate of ammonia (NH
4HCO
3) 15～20g/L and methane amide 150～200ml/L; Said components added in the distilled water dissolve, regulate pH value to 8.3～9.5, make sand copper facing plating bath;
(2) the thick compound plating plating bath of sand of going up of configuration: will put into the last sand coating bath that sand copper facing plating bath is housed through the fine diamond particle of surface preparation, whenever going up the fine diamond grain amount that sand copper facing plating bath added is 30～40 grams, soaked 20～36 hours, and obtained the compound plating of copper-diamond and slightly go up the sand plating bath;
(3) the thin compound plating plating bath of sand of going up of configuration: will put into the last sand coating bath that sand copper facing plating bath is housed through the brait particle of surface preparation, whenever going up the brait grain amount that sand copper facing plating bath added is 10～15 grams, soaked 20～24 hours, and obtained the compound plating of copper-diamond and carefully go up the sand plating bath;
(4) copper electrolyte is reinforced in preparation: described reinforcing copper electrolyte comprises following component by mass volume ratio: cupric fluoborate (Cu (BF
4)
2.6H
2O) 500～520g/L, fluoroboric acid chromium (Cr (BF
4)
3.4H
2O) 145～160g/L, fluoroboric acid (HBF
440%) 40～45ml/L and boric acid (HBO
3) 20～25g/L; Said components added in the distilled water dissolve, regulate pH value to 0.5～0.7, make the reinforcing copper electrolyte, gained is reinforced copper electrolyte be contained in the reinforcing coating bath standby;
(5) with workpiece surface after mechanical treatment and matting, put into the thick sand coating bath of going up that the sand plating bath is slightly gone up in the compound plating of copper-diamond be housed, adopt and bury sand on the sand method, current density is 0.4～1A/dm
2, slightly going up the sand plating time is 15～35 minutes, obtains being coated with the compound workpiece of going up sand coating of copper-diamond;
(6) will be coated with the compound workpiece of going up sand coating of copper-diamond and put into reinforcing coating bath electro-coppering back-up coat, current density is 13～17A/dm
2, reinforce to the diamond particles height 80～90% after, take out workpiece, flushing is dry;
(7) will reinforce workpiece after the plating and put into and the compound plating of copper-diamond is housed carefully goes up sand coating bath on sand plating bath thin, and carefully go up sand with suspension method, current density is 0.5～1A/dm
2, carefully go up sand plating 3～7 minutes, carefully going up sand layer thickness is 1.0～1.5 μ m, it highly is 1.5～0.5 μ m that diamond is appeared, and obtains depositing the workpiece of copper-diamond composite deposite.
The described brait particulate of step (2) size range is W10～W15 (being that particle diameter is 10～15 μ m); Described surface preparation is according to the following steps: place the concentrated hydrochloric acid of 25～36wt.% to boil 30～60 minutes the brait particle, wash with water then to neutrality, obtain the brait particle through surface preparation; The described fine diamond particulate of step (3) size range is W1.0～W1.5 (being that particle diameter is 1.0～1.5 μ m), described surface preparation is according to the following steps: place the concentrated hydrochloric acid of 25～36wt.% to boil 20～40min the fine diamond particle, wash with water then to neutrality, obtain fine diamond particle through surface preparation.
The described workpiece of step (5) is a copper sheet, and described mechanical treatment is through the scrubbing of 1000# coated abrasive working with workpiece surface; Described matting is to be ultrasonic cleaning 10～30 minutes in 8～10% the sodium hydroxide solution with workpiece at massfraction, cleans 3～5 minutes with hydrochloric acid then, washes with water clean at last.
Step (5) is described buries the sand method by following operation steps: fully stir the compound plating of copper-diamond earlier and slightly go up the sand plating bath, diamond particles is dispersed evenly in the sand copper facing plating bath, again workpiece is lain in a horizontal plane in the thick sand coating bath bottom of going up, left standstill 1～10 minute, diamond particles is covered workpiece surface, and the copper of being separated out by negative electrode near the diamond particles of workpiece surface during plating embeds in the coating.
Owing to reinforce the fluoroboric acid chromium that contains higher concentration in the plating bath, make in the copper on the workpiece after step (6) gained is reinforced plating and contain 0.2～0.3wt.%Cr, can significantly improve Cu and adamantine adhesion property, and very little to the influence of thermal conductivity and resistivity.
The described suspension method of step (7) carefully goes up sand and presses following operation steps: fully stir the compound plating of copper-diamond earlier and carefully go up the sand plating bath, the fine diamond uniform particles is suspended in the sand copper facing plating bath, the workpiece that to reinforce again after plating vertically is placed on thin going up in the sand coating bath, and the copper of being separated out by negative electrode near the diamond particles of workpiece surface during plating embeds in the coating.The purpose that step (7) carefully goes up sand is to improve the diamond density of appearing, and when making later CVD isoepitaxial growth, can form continuous film as early as possible, and reduce the interface hole.
Described second step specifically comprises following operation steps:
A, the workpiece that will deposit the copper-diamond composite deposite are inserted in the CVD diamond deposition system, when being evacuated to 1.0～0.01Pa, feed High Purity Hydrogen, and startup CVD cracking thermal source, form hydrogen plasma flame stream, workpiece is carried out hydrogen plasma etching 1.0～2.0h (this step purpose is for impurity such as graphite that cleans Cu-diamond composite plating laminar surface and amorphous carbons);
B, adjust temperature to 850～900 ℃, feed the high-purity methane of 0.8～1.5vol.%, the appear diamond surface epitaxy diamond of beginning in the copper-diamond composite deposite is when epitaxy diamond film thickness surpasses 20 μ m, stop to import methane, keep the hydrogen plasma flame flow;
C, progressively reduce hydrogen plasma flame flow power and temperature-control circuit power, workpiece slowly is cooled to below 100 ℃ with the speed of 3～5 ℃/min, stop to feed High Purity Hydrogen, make vacuum up to 1.0～0.01Pa, close hydrogen plasma flame flow power and temperature-control circuit power power-supply at last, after workpiece is as cold as room temperature with stove, take out workpiece, obtain copper base pattern structure interface diamond coatings.
The described CVD diamond deposition of steps A system is that heated filament CVD system, microwave CVD system or direct current plasma spray the CVD system.
The described sample temperature of step B need be strict controlled in 850～900 ℃ of scopes, the too high meeting of temperature is mixed in the diamond film Cu steam, reduce the quality of diamond film, temperature is crossed low meeting increases amorphous carbon content in the diamond film, the same quality that reduces diamond film, these all reduce the thermal conductivity of diamond film.
During the diamond epitaxy because of the sample temperature height, to spread fully between Cu-diamond composite deposite and matrix and composite deposite and diamond, electroplate defective (as electroplating stress, hole, segregation etc.) basically eliminate, composite deposite and former Cu matrix diffuse to integrated.
The purpose of slowly cooling off sample in the step (3) is to reduce sample to form thermal stresses in process of cooling as far as possible, to improve the thermal conductivity of diamond coatings.
Above-mentioned copper base pattern structure interface diamond coatings is applied to prepare the microelectronics heat sink material.
The relative prior art of the present invention has following advantage and beneficial effect:
The present invention can successfully prepare and the firm diamond film of matrix bond on the Cu matrix, continuous texture diamond film because of the part isoepitaxial growth one-tenth of in the CVD process, appearing, the temperature and time of CVD growth simultaneously makes mutual diffusion mutually between composite deposite and the basal body interface, defective in the electrolytic coating is at utmost eliminated, electroplating Cu and matrix Cu fully spreads, it is integrated that matrix and electrolytic coating are fully spread, the Cu-diamond composite deposite has reduced thermal expansivity significantly, the thermal stresses of diamond coatings is significantly reduced, the mutual interlock of pattern structure interface diamond coatings and matrix, the interface contact area increases, and significantly increases with the bonding force of Cu matrix.Pattern structure interface diamond coatings can obtain and the firm bonding force of Cu matrix on the Cu matrix, the pressing in method check, and under 294N load, indentation edge is not seen disbonding, demonstrates and matrix good binding performance.Copper base of the present invention inlays that pattern structure interface diamond is coated with the purity height, impurity is few, and thermal stresses is low, and is firm with matrix bond, is that the ideal of microelectronics heat sink material is selected.
Description of drawings
Fig. 1 is the sand plating appts synoptic diagram on the sand method that buries of preparation copper-diamond composite deposite of the present invention, and wherein 1 is horizontal positioned workpiece (negative electrode), and 2 is last sand copper facing plating bath, 3 is the horizontal positioned pure copper anode, 4 is adjustable direct supply, and 5 is diamond particles, and 6 is DC ammeter.
Fig. 2 is the 294N impression photo figure of copper base pattern structure of the present invention interface diamond coatings, and indentation edge does not come off substantially.
Fig. 3 is the 294N indentation edge high power SEM photo figure of copper base pattern structure of the present invention interface diamond coatings, and the edge does not see that crackle outwards expands.
Fig. 4 is the Raman spectrogram of copper base pattern structure of the present invention interface diamond coatings, shows diamond coatings purity height, and impurity such as amorphous carbon seldom.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but the working of an invention mode is not limited thereto.
The first step: the thick sand+Cu that goes up of preparation reinforce+carefully goes up the sand composite deposite:
(1) sand copper facing plating bath in the preparation: get citric acid 27 gram and ventilation breather 6 and restrain and be dissolved in successively in the A beaker that fills 80ml distilled water, getting bicarbonate of ammonia 3.6 gram and ethylenediamine tetraacetic acid (EDTA) 3.0 restrains and is dissolved in successively in the B beaker that fills 40ml distilled water, solution with the B beaker after the dissolving fully slowly adds in the A beaker, getting Seignette salt 9.0 grams adds in the A beaker, measure methane amide 30ml and add the A beaker, then regulate pH value to 8.3～9.5 with sodium hydroxide, preparation 200ml goes up sand copper facing plating bath, the prepared sand copper facing plating bath of going up is divided in A beaker and the B beaker, every is 100ml, standby;
(2) the thick compound plating plating bath of sand of going up of configuration: with granularity is the diamond particles of W10 (9～10 μ m), be in stink cupboard, to boil 30min in 36% the hydrochloric acid with massfraction, extremely neutral with the distilled water rinsing, get 3g and put into the A beaker, soak after 36 hours, obtain the compound plating of copper-diamond and slightly go up the sand plating bath;
(3) the thin compound plating plating bath of sand of going up of configuration: with granularity is the diamond particles of W1.0 (0.9～1.0 μ m), be in stink cupboard, to boil 20min in 36% the hydrochloric acid with massfraction, extremely neutral with the distilled water rinsing, get 1.0g and put into the B beaker, soak after 24 hours, obtain the compound plating of copper-diamond and carefully go up the sand plating bath;
(4) copper electrolyte is reinforced in preparation: take by weighing cupric fluoborate (Cu (BF
4)
2.6H
2O) 50g, fluoroboric acid chromium (Cr (BF
4)
3.4H
2O) 15g, boric acid (HBO
3) 2.2g dissolves and be equipped with in the C beaker of 50ml distilled water successively, measures fluoroboric acid (HBF
440%) in 4ml to the C beaker, regulates pH value to 0.5～0.7, add distilled water, make standby copper and reinforce plating bath to 100ml;
(5) make workpiece with the copper sheet of 10 * 20mm, electroless plating face (back side) is protected with insullac, copper sheet is plated preceding cleaning after mechanical mill, polishing, be about to copper sheet to place massfraction be 10% aqueous sodium hydroxide solution the greasy dirt on copper sheet surface is removed with ultrasonic cleaning 10 minutes; Cleaned 5 minutes with hydrochloric acid then, make the copper sheet surface active; Use dehydration of alcohol again, seasoning; Put into the thick sand plating beaker A bottom of going up, sand faces up on the needs; Pure copper anode is placed on directly over the copper sheet, leaves standstill 3 minutes, makes the copper sheet surface deposition that one deck diamond particles be arranged, and sand plating appts is used current density 0.8A/dm as shown in Figure 1 on it
2Take out copper sheet behind the plating 20min, fall to fail to plate firm bortz powder with distilled water flushing;
(6) will slightly go up sample after the sand plating and insert and be equipped with in the B beaker of reinforcing plating plating plating bath, need surfacing over against anode, use current density 15A/dm
2Electroplate 10min, take out copper sheet, oven dry, under opticmicroscope or scanning electronic microscope, observe the adamantine situation of lifting one's head in the coating, make diamond particles lift one's head about 1.5 μ m, the too many needs of lifting one's head are mended plating, and the salpeter solution of too little then available volume percentage concentration 32% of lifting one's head is partly dissolved; After plated film finishes, take out workpiece, with distilled water flushing clean back oven dry;
(7) workpiece that will reinforce after plating places the thin C beaker of going up the sand plating, fully stirs plating bath, and the fine diamond powder is fully suspended, and needs surfacing over against anode, uses 0.6A/dm
2Plating 4min takes out the flushing oven dry, obtains slightly going up on the Cu matrix sand+Cu and reinforce+carefully goes up the composite deposite of sand, promptly obtain depositing the workpiece of copper-diamond composite deposite.
Second step: heated filament CVD isoepitaxial growth diamond:
(1) will deposit and thick go up the workpiece that sand+Cu reinforce+carefully goes up sand and place under the tungsten filament of heated filament CVD system, filament and sample surfaces distance are 5mm, after being evacuated to 1Pa, feed 100sccm (the ml/min flow under the normal conditions) High Purity Hydrogen and fill that to keep system's vacuum tightness behind the hydrogen be 2.0KPa, connect the tungsten filament power supply, slow rising tungsten filament temperature to 2000 ℃ (measurement of optical radiation pyrometer), sample temperature is between 700～750 ℃, hydrogen flows through that the elevated temperature heat filament becomes please plasma body and etching sample surfaces, and etching time is 1.0h;
(2) adjusting hydrogen flowing quantity is 99sccm, and vacuum tightness is adjusted into 5.0KPa, feeds 1.0sccm methane, connects sample and adds electrothermal stove, makes sample temperature be elevated to 850 ℃, beginning isoepitaxial growth diamond coatings.Growth time is 40h, and diamond isoepitaxial growth thickness is about 25 μ m.Can close methane this moment, stops epitaxy;
(3) progressively reduce the tungsten filament electric current, keep hydrogen flowing quantity, sample slowly is cooled to below 100 ℃ with the speed of 3～5 ℃/min, close hydrogen then, make vacuum up, close all thermal power power supplys at last, after sample is as cold as room temperature with stove, open vacuum chamber, take out sample, obtain pattern structure interface diamond coatings on the Cu matrix.
The 294N impression photo figure of gained copper base pattern structure interface diamond coatings as shown in Figure 2;
The 294N indentation edge high power SEM photo figure of gained copper base pattern structure interface diamond coatings as shown in Figure 3;
The Raman spectrogram of copper base pattern structure interface diamond coatings shows diamond coatings purity height as shown in Figure 4, and impurity such as amorphous carbon seldom.
Pattern structure interface diamond coatings is (111) columnar crystal structure on the prepared Cu matrix, and the Raman spectral test is the result show, diamond film purity is very high, and internal stress is very low; Under 294N Rockwell hardness impression, impression diameter is 540 μ m, and indentation edge is not seen the diamond coatings avalanche, does not see crackle extending transversely yet, shows that diamond coatings and basal body binding force are very high.
The first step: the thick sand+Cu that goes up of preparation reinforce+carefully goes up the sand composite deposite:
(1) sand copper facing plating bath in the preparation: get citric acid 27 gram and ventilation breather 6 and restrain and be dissolved in successively in the A beaker that fills 80ml distilled water, getting bicarbonate of ammonia 3.6 gram and ethylenediamine tetraacetic acid (EDTA) 3.0 restrains and is dissolved in successively in the B beaker that fills 40ml distilled water, solution with the B beaker after the dissolving fully slowly adds in the A beaker, getting Seignette salt 9.0 grams adds in the A beaker, measure methane amide 30ml and add the A beaker, then regulate pH value to 8.3～9.5 with sodium hydroxide, preparation 200ml goes up sand copper facing plating bath, the prepared sand copper facing plating bath of going up is divided in A beaker and the B beaker, every is 100ml, standby;
(2) the thick compound plating plating bath of sand of going up of configuration: with granularity is the diamond particles of W15 (14～15 μ m), be in stink cupboard, to boil 30min in 36% the hydrochloric acid with massfraction, extremely neutral with the distilled water rinsing, get 4g and put into the A beaker, soak after 36 hours, obtain the compound plating of copper-diamond and slightly go up the sand plating bath;
(3) the thin compound plating plating bath of sand of going up of configuration: with granularity is the diamond particles of W1.5 (1.3～1.5 μ m), be in stink cupboard, to boil 25min in 36% the hydrochloric acid with massfraction, extremely neutral with the distilled water rinsing, get 1.5g and put into the B beaker, soak after 24 hours, obtain the compound plating of copper-diamond and carefully go up the sand plating bath;
(4) copper electrolyte is reinforced in preparation: take by weighing cupric fluoborate (Cu (BF
4)
2.6H
2O) 50g, fluoroboric acid chromium (Cr (BF
4)
3.4H
2O) 15g, boric acid (HBO
3) 2.2g dissolves and be equipped with in the C beaker of 50ml distilled water successively, measures fluoroboric acid (HBF
440%) in 4ml to the C beaker, regulates pH value to 0.5～0.7, add distilled water, make standby copper and reinforce plating bath to 100ml;
(5) make workpiece with the copper sheet of 10 * 20mm, electroless plating face (back side) is protected with insullac, copper sheet is plated preceding cleaning after mechanical mill, polishing, be about to copper sheet to place massfraction be 10% aqueous sodium hydroxide solution the greasy dirt on copper sheet surface is removed with ultrasonic cleaning 10 minutes; Cleaned 5 minutes with hydrochloric acid then, make the copper sheet surface active; Use dehydration of alcohol again, seasoning; Put into the thick sand plating beaker A bottom of going up, sand faces up on the needs; Pure copper anode is placed on directly over the copper sheet, leaves standstill 3 minutes, makes the copper sheet surface deposition that one deck diamond particles be arranged, and sand plating appts is used current density 0.8A/dm as shown in Figure 1 on it
2Take out copper sheet behind the plating 30min, fall to fail to plate firm bortz powder with distilled water flushing;
(6) will slightly go up workpiece after the sand plating and insert and be equipped with in the B beaker of reinforcing plating plating plating bath, need surfacing over against anode, use current density 15A/dm
2Electroplate 10min, take out copper sheet, oven dry, under opticmicroscope or scanning electronic microscope, observe the adamantine situation of lifting one's head in the coating, make diamond particles lift one's head about 1.5 μ m, the too many needs of lifting one's head are mended plating, and the salpeter solution of too little then available volume percentage concentration 32% of lifting one's head is partly dissolved; After plated film finishes, take out workpiece, with distilled water flushing clean back oven dry;
(7) workpiece that will reinforce after plating places the thin C beaker of going up the sand plating, fully stirs plating bath, and the fine diamond powder is fully suspended, and needs surfacing over against anode, uses 0.8A/dm
2Plating 6min takes out the flushing oven dry, obtains slightly going up on the Cu matrix sand+Cu and reinforce+carefully goes up the composite deposite of sand, promptly obtain depositing the workpiece of copper-diamond composite deposite.
Second step: heated filament CVD isoepitaxial growth diamond:
(1) will deposit and thick go up the workpiece that sand+Cu reinforce+carefully goes up sand and place under the tungsten filament of heated filament CVD system, filament and sample surfaces distance are 5mm, after being evacuated to 1Pa, feed 100sccm (the ml/min flow under the normal conditions) High Purity Hydrogen and fill that to keep system's vacuum tightness behind the hydrogen be 2.0KPa, connect the tungsten filament power supply, slow rising tungsten filament temperature to 2000 ℃ (measurement of optical radiation pyrometer), sample temperature is between 700～750 ℃, hydrogen flows through that the elevated temperature heat filament becomes please plasma body and etching sample surfaces, and etching time is 1.0h;
(2) adjusting hydrogen flowing quantity is 99sccm, and vacuum tightness is adjusted into 5.0KPa, feeds 1.0sccm methane, connects sample and adds electrothermal stove, makes sample temperature be elevated to 850 ℃, beginning isoepitaxial growth diamond coatings.Growth time is 40h, and diamond isoepitaxial growth thickness is about 26 μ m.Can close methane this moment, stops epitaxy;
(3) progressively reduce the tungsten filament electric current, keep hydrogen flowing quantity, sample slowly is cooled to below 100 ℃ with the speed of 3～5 ℃/min, close hydrogen then, make vacuum up, close all thermal power power supplys at last, after sample is as cold as room temperature with stove, open vacuum chamber, take out sample, obtain pattern structure interface diamond coatings on the Cu matrix.
Pattern structure interface diamond coatings is (111) columnar crystal structure on the prepared Cu matrix, and the Raman spectral test is the result show, diamond film purity is very high, and internal stress is very low; Under 294N Rockwell hardness impression, impression diameter is 460 μ m, little than example 1, and indentation edge is not seen the diamond coatings avalanche, does not see crackle extending transversely yet, shows that diamond coatings and basal body binding force are very high.
The first step: the thick sand+Cu that goes up of preparation reinforce+carefully goes up the sand composite deposite:
(1) sand copper facing plating bath in the preparation: get citric acid 27 gram and ventilation breather 6 and restrain and be dissolved in successively in the A beaker that fills 80ml distilled water, getting bicarbonate of ammonia 3.6 gram and ethylenediamine tetraacetic acid (EDTA) 3.0 restrains and is dissolved in successively in the B beaker that fills 40ml distilled water, solution with the B beaker after the dissolving fully slowly adds in the A beaker, getting Seignette salt 9.0 grams adds in the A beaker, measure methane amide 30ml and add the A beaker, then regulate pH value to 8.3～9.5 with sodium hydroxide, preparation 200ml goes up sand copper facing plating bath, the prepared sand copper facing plating bath of going up is divided in A beaker and the B beaker, every is 100ml, standby;
(2) the thick compound plating plating bath of sand of going up of configuration: with granularity is the diamond particles of W10 (9～10 μ m), be in stink cupboard, to boil 30min in 36% the hydrochloric acid with massfraction, extremely neutral with the distilled water rinsing, get 3g and put into the A beaker, soak after 36 hours, obtain the compound plating of copper-diamond and slightly go up the sand plating bath;
(3) the thin compound plating plating bath of sand of going up of configuration: with granularity is the diamond particles of W1.5 (1.3～1.5 μ m), be in stink cupboard, to boil 25min in 36% the hydrochloric acid with massfraction, extremely neutral with the distilled water rinsing, get 1.5g and put into the B beaker, soak after 24 hours, obtain the compound plating of copper-diamond and carefully go up the sand plating bath;
(4) copper electrolyte is reinforced in preparation: take by weighing cupric fluoborate (Cu (BF
4)
2.6H
2O) 50g, fluoroboric acid chromium (Cr (BF
4)
3.4H
2O) 15g, boric acid (HBO
3) 2.2g dissolves and be equipped with in the C beaker of 50ml distilled water successively, measures fluoroboric acid (HBF
440%) in 4ml to the C beaker, regulates pH value to 0.5～0.7, add distilled water, make standby copper and reinforce plating bath to 100ml;
(5) make workpiece with the copper sheet of 10 * 20mm, electroless plating face (back side) is protected with insullac, copper sheet is plated preceding cleaning after mechanical mill, polishing, be about to copper sheet to place massfraction be 10% aqueous sodium hydroxide solution the greasy dirt on copper sheet surface is removed with ultrasonic cleaning 10 minutes; Cleaned 5 minutes with hydrochloric acid then, make the copper sheet surface active; Use dehydration of alcohol again, seasoning; Put into the thick sand plating beaker A bottom of going up, sand faces up on the needs; Pure copper anode is placed on directly over the copper sheet, leaves standstill 3 minutes, makes the copper sheet surface deposition that one deck diamond particles be arranged, and sand plating appts is used current density 0.8A/dm as shown in Figure 1 on it
2Take out copper sheet behind the plating 30min, fall to fail to plate firm bortz powder with distilled water flushing;
(6) will slightly go up workpiece after the sand plating and insert and be equipped with in the B beaker of reinforcing plating plating plating bath, need surfacing over against anode, use current density 15A/dm
2Electroplate 10min, take out copper sheet, oven dry, under opticmicroscope or scanning electronic microscope, observe the adamantine situation of lifting one's head in the coating, make diamond particles lift one's head about 1.5 μ m, the too many needs of lifting one's head are mended plating, and the salpeter solution of too little then available volume percentage concentration 32% of lifting one's head is partly dissolved; After plated film finishes, take out workpiece, with distilled water flushing clean back oven dry;
(7) workpiece that will reinforce after plating places the thin C beaker of going up the sand plating, fully stirs plating bath, and the fine diamond powder is fully suspended, and needs surfacing over against anode, uses 0.8A/dm
2Plating 6min takes out the flushing oven dry, obtains slightly going up on the Cu matrix sand+Cu and reinforce+carefully goes up the composite deposite of sand, promptly obtain depositing the workpiece of copper-diamond composite deposite.
Second step: heated filament CVD isoepitaxial growth diamond:
(1) will deposit and thick go up the workpiece that sand+Cu reinforce+carefully goes up sand and place under the tungsten filament of heated filament CVD system, filament and sample surfaces distance are 5mm, after being evacuated to 1Pa, feed 100sccm (the ml/min flow under the normal conditions) High Purity Hydrogen and fill that to keep system's vacuum tightness behind the hydrogen be 2.0KPa, connect the tungsten filament power supply, slow rising tungsten filament temperature to 2000 ℃ (measurement of optical radiation pyrometer), sample temperature is between 700～750 ℃, hydrogen flows through that the elevated temperature heat filament becomes please plasma body and etching sample surfaces, and etching time is 1.0h;
(2) adjusting hydrogen flowing quantity is 99sccm, and vacuum tightness is adjusted into 5.0KPa, feeds 1.0sccm methane, connects sample and adds electrothermal stove, makes sample temperature be elevated to 900 ℃, beginning isoepitaxial growth diamond coatings.Growth time is 40h, and diamond isoepitaxial growth thickness is about 32 μ m, and diamond coatings thickness is greatly because sample temperature is higher than example 1 and example 2, due to the speed of growth is very fast.Can close methane this moment, stops epitaxy;
(3) progressively reduce the tungsten filament electric current, keep hydrogen flowing quantity, sample slowly is cooled to below 100 ℃ with the speed of 3～5 ℃/min, close hydrogen then, make vacuum up, close all thermal power power supplys at last, after sample is as cold as room temperature with stove, open vacuum chamber, take out sample, obtain pattern structure interface diamond coatings on the Cu matrix.
Pattern structure interface diamond coatings is (111) columnar crystal structure on the prepared Cu matrix, and the Raman spectral test is the result show, diamond film purity is very high, and internal stress is very low; Under 294N Rockwell hardness impression, impression diameter is 518 μ m, and indentation edge is not seen the diamond coatings avalanche, does not see crackle extending transversely yet, shows that diamond coatings and basal body binding force are very high.
The first step: the thick sand+Cu that goes up of preparation reinforce+carefully goes up the sand composite deposite:
(1) sand copper facing plating bath in the preparation: get citric acid 27 gram and ventilation breather 6 and restrain and be dissolved in successively in the A beaker that fills 80ml distilled water, getting bicarbonate of ammonia 3.6 gram and ethylenediamine tetraacetic acid (EDTA) 3.0 restrains and is dissolved in successively in the B beaker that fills 40ml distilled water, solution with the B beaker after the dissolving fully slowly adds in the A beaker, getting Seignette salt 9.0 grams adds in the A beaker, measure methane amide 30ml and add the A beaker, then regulate pH value to 8.3～9.5 with sodium hydroxide, preparation 200ml goes up sand copper facing plating bath, the prepared sand copper facing plating bath of going up is divided in A beaker and the B beaker, every is 100ml, standby;
(2) the thick compound plating plating bath of sand of going up of configuration: with granularity is the diamond particles of W15 (14～15 μ m), be in stink cupboard, to boil 30min in 36% the hydrochloric acid with massfraction, extremely neutral with the distilled water rinsing, get 3g and put into the A beaker, soak after 36 hours, obtain the compound plating of copper-diamond and slightly go up the sand plating bath;
(3) the thin compound plating plating bath of sand of going up of configuration: with granularity is the diamond particles of W1.5 (1.3～1.5 μ m), be in stink cupboard, to boil 25min in 36% the hydrochloric acid with massfraction, extremely neutral with the distilled water rinsing, get 1.5g and put into the B beaker, soak after 24 hours, obtain the compound plating of copper-diamond and carefully go up the sand plating bath;
(4) copper electrolyte is reinforced in preparation: take by weighing cupric fluoborate (Cu (BF
4)
2.6H
2O) 50g, fluoroboric acid chromium (Cr (BF
4)
3.4H
2O) 15g, boric acid (HBO
3) 2.2g dissolves and be equipped with in the C beaker of 50ml distilled water successively, measures fluoroboric acid (HBF
440%) in 4ml to the C beaker, regulates pH value to 0.5～0.7, add distilled water, make standby copper and reinforce plating bath to 100ml;
(5) make workpiece with the copper sheet of 10 * 20mm, electroless plating face (back side) is protected with insullac, copper sheet is plated preceding cleaning after mechanical mill, polishing, be about to copper sheet to place massfraction be 10% aqueous sodium hydroxide solution the greasy dirt on copper sheet surface is removed with ultrasonic cleaning 10 minutes; Cleaned 5 minutes with hydrochloric acid then, make the copper sheet surface active; Use dehydration of alcohol again, seasoning; Put into the thick sand plating beaker A bottom of going up, sand faces up on the needs; Pure copper anode is placed on directly over the copper sheet, leaves standstill 3 minutes, makes the copper sheet surface deposition that one deck diamond particles be arranged, and sand plating appts is used current density 0.8A/dm as shown in Figure 1 on it
2Take out copper sheet behind the plating 30min, fall to fail to plate firm bortz powder with distilled water flushing;
(6) will slightly go up workpiece after the sand plating and insert and be equipped with in the B beaker of reinforcing plating plating plating bath, need surfacing over against anode, use current density 15A/dm
2Electroplate 10min, take out copper sheet, oven dry, under opticmicroscope or scanning electronic microscope, observe the adamantine situation of lifting one's head in the coating, make diamond particles lift one's head about 1.5 μ m, the too many needs of lifting one's head are mended plating, and the salpeter solution of too little then available volume percentage concentration 32% of lifting one's head is partly dissolved; After plated film finishes, take out workpiece, with distilled water flushing clean back oven dry;
(7) workpiece that will reinforce after plating places the thin C beaker of going up the sand plating, fully stirs plating bath, and the fine diamond powder is fully suspended, and needs surfacing over against anode, uses 0.8A/dm
2Plating 6min takes out the flushing oven dry, obtains slightly going up on the Cu matrix sand+Cu and reinforce+carefully goes up the composite deposite of sand, promptly obtain depositing the workpiece of copper-diamond composite deposite.
Second step: heated filament CVD isoepitaxial growth diamond:
(1) will deposit and thick go up the workpiece that sand+Cu reinforce+carefully goes up sand and place under the tungsten filament of heated filament CVD system, filament and sample surfaces distance are 5mm, after being evacuated to 1Pa, feed 100sccm (the ml/min flow under the normal conditions) High Purity Hydrogen and fill that to keep system's vacuum tightness behind the hydrogen be 2.0KPa, connect the tungsten filament power supply, slow rising tungsten filament temperature to 2000 ℃ (measurement of optical radiation pyrometer), sample temperature is between 700～750 ℃, hydrogen flows through that the elevated temperature heat filament becomes please plasma body and etching sample surfaces, and etching time is 1.0h;
(2) adjusting hydrogen flowing quantity is 99sccm, and vacuum tightness is adjusted into 5.0KPa, feeds 1.0sccm methane, connects sample and adds electrothermal stove, makes sample temperature be elevated to 900 ℃, beginning isoepitaxial growth diamond coatings.Growth time is 40h, and diamond isoepitaxial growth thickness is about 33.5 μ m, and diamond coatings thickness is greatly because sample temperature is higher than example 1 and example 2, due to the speed of growth is very fast.Can close methane this moment, stops epitaxy;
(3) progressively reduce the tungsten filament electric current, keep hydrogen flowing quantity, sample slowly is cooled to below 100 ℃ with the speed of 3～5 ℃/min, close hydrogen then, make vacuum up, close all thermal power power supplys at last, after sample is as cold as room temperature with stove, open vacuum chamber, take out sample, obtain pattern structure interface diamond coatings on the Cu matrix.
Pattern structure interface diamond coatings is (111) columnar crystal structure on the prepared Cu matrix, and the Raman spectral test is the result show, diamond film purity is very high, and internal stress is very low; Under 294N Rockwell hardness impression, impression diameter is 502 μ m, and indentation edge is not seen the diamond coatings avalanche, does not see crackle extending transversely yet, shows that diamond coatings and basal body binding force are very high.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. copper base pattern structure interface diamond coatings is characterized in that: described copper base pattern structure interface diamond coatings slightly goes up that sand coating, copper back-up coat, copper-diamond are compound carefully to be gone up layer of sand and form at CVD diamond epitaxially grown layer by copper-diamond is compound from top to bottom; Contain trace Cr in the described copper back-up coat.
2. the preparation method of a kind of copper base pattern structure according to claim 1 interface diamond coatings, it is characterized in that may further comprise the steps: the first step, deposit successively on the copper matrix copper-diamond compound thick on sand coating, copper back-up coat and copper-diamond compound thin on layer of sand, obtain depositing the workpiece of copper-diamond composite deposite; In second step, in CVD diamond deposition system, isoepitaxial growth goes out the successive diamond coatings on the diamond that the workpiece surface that deposits the copper-diamond composite deposite is appeared.
3. the preparation method of a kind of copper base pattern structure according to claim 2 interface diamond coatings, it is characterized in that: the described the first step specifically comprises following operation steps:
(1) sand copper facing plating bath in the preparation: the described sand copper facing plating bath of going up comprises following component by mass volume ratio: ventilation breather 55～65g/L, ethylenediamine tetraacetic acid (EDTA) 10～20g/L, citric acid 250～290g/L, Seignette salt 40～50g/L, bicarbonate of ammonia 15～20g/L and methane amide 150～200ml/L; Said components added in the distilled water dissolve, regulate pH value to 8.3～9.5, make sand copper facing plating bath;
(2) the thick compound plating plating bath of sand of going up of configuration: will put into the last sand coating bath that sand copper facing plating bath is housed through the fine diamond particle of surface preparation, whenever going up the fine diamond grain amount that sand copper facing plating bath added is 30～40 grams, soaked 20～36 hours, and obtained the compound plating of copper-diamond and slightly go up the sand plating bath;
(3) the thin compound plating plating bath of sand of going up of configuration: will put into the last sand coating bath that sand copper facing plating bath is housed through the brait particle of surface preparation, whenever going up the brait grain amount that sand copper facing plating bath added is 10～15 grams, soaked 20～24 hours, and obtained the compound plating of copper-diamond and carefully go up the sand plating bath;
(4) copper electrolyte is reinforced in preparation: described reinforcing copper electrolyte comprises following component by mass volume ratio: cupric fluoborate 500～520g/L, fluoroboric acid chromium 145～160g/L, fluoroboric acid 40～45ml/L and boric acid 20～25g/L; Said components added in the distilled water dissolve, regulate pH value to 0.5～0.7, make the reinforcing copper electrolyte, gained is reinforced copper electrolyte be contained in the reinforcing coating bath standby;
(5) with workpiece surface after mechanical treatment and matting, put into the thick sand coating bath of going up that the sand plating bath is slightly gone up in the compound plating of copper-diamond be housed, adopt and bury sand on the sand method, current density is 0.4～1A/dm
2, slightly going up the sand plating time is 15～35 minutes, obtains being coated with the compound workpiece of going up sand coating of copper-diamond;
(6) will be coated with the compound workpiece of going up sand coating of copper-diamond and put into reinforcing coating bath electro-coppering back-up coat, current density is 13～17A/dm
2, reinforce to the diamond particles height 80～90% after, take out workpiece, flushing is dry;
(7) will reinforce workpiece after the plating and put into and the compound plating of copper-diamond is housed carefully goes up sand coating bath on sand plating bath thin, and carefully go up sand with suspension method, current density is 0.5～1A/dm
2, carefully go up sand plating 3～7 minutes, carefully going up sand layer thickness is 1.0～1.5 μ m, it highly is 1.5～0.5 μ m that diamond is appeared, and obtains depositing the workpiece of copper-diamond composite deposite.
4. the preparation method of a kind of copper base pattern structure according to claim 3 interface diamond coatings, it is characterized in that: the described brait particulate of step (2) size range is W10～W15; Described surface preparation is according to the following steps: place the concentrated hydrochloric acid of 25～36wt.% to boil 30～60 minutes the brait particle, wash with water then to neutrality, obtain the brait particle through surface preparation; The described fine diamond particulate of step (3) size range is W1.0～W1.5, described surface preparation is according to the following steps: place the concentrated hydrochloric acid of 25～36wt.% to boil 20～40min the fine diamond particle, wash with water then to neutrality, obtain fine diamond particle through surface preparation.
5. the preparation method of a kind of copper base pattern structure according to claim 3 interface diamond coatings, it is characterized in that: the described workpiece of step (5) is a copper sheet, described mechanical treatment is through the scrubbing of 1000# coated abrasive working with workpiece surface; Described matting is to be ultrasonic cleaning 10～30 minutes in 8～10% the sodium hydroxide solution with workpiece at massfraction, cleans 3～5 minutes with hydrochloric acid then, washes with water clean at last.
6. the preparation method of a kind of copper base pattern structure according to claim 3 interface diamond coatings, it is characterized in that: step (5) is described buries the sand method by following operation steps: fully stir the compound plating of copper-diamond earlier and slightly go up the sand plating bath, diamond particles is dispersed evenly in the sand copper facing plating bath, again workpiece is lain in a horizontal plane in the thick sand coating bath bottom of going up, left standstill 1～10 minute, diamond particles is covered workpiece surface, and the copper of being separated out by negative electrode near the diamond particles of workpiece surface during plating embeds in the coating.
7. the preparation method of a kind of copper base pattern structure according to claim 3 interface diamond coatings, it is characterized in that: the described suspension method of step (7) carefully goes up sand and presses following operation steps: fully stir the compound plating of copper-diamond earlier and carefully go up the sand plating bath, the fine diamond uniform particles is suspended in the sand copper facing plating bath, the workpiece that to reinforce again after plating vertically is placed on thin going up in the sand coating bath, and the copper of being separated out by negative electrode near the diamond particles of workpiece surface during plating embeds in the coating.
8. the preparation method of a kind of copper base pattern structure according to claim 1 interface diamond coatings is characterized in that: described second step specifically comprises following operation steps:
A, the workpiece that will deposit the copper-diamond composite deposite are inserted in the CVD diamond deposition system, when being evacuated to 1.0～0.01Pa, feed High Purity Hydrogen, and start CVD cracking thermal source, form hydrogen plasma flame stream, workpiece is carried out hydrogen plasma etching 1.0～2.0h;
B, adjust temperature to 850～900 ℃, feed the high-purity methane of 0.8～1.5vol.%, the appear diamond surface epitaxy diamond of beginning in the copper-diamond composite deposite is when epitaxy diamond film thickness surpasses 20 μ m, stop to import methane, keep the hydrogen plasma flame flow;
C, progressively reduce hydrogen plasma flame flow power and temperature-control circuit power, workpiece slowly is cooled to below 100 ℃ with the speed of 3～5 ℃/min, stop to feed High Purity Hydrogen, make vacuum up to 1.0～0.01Pa, close hydrogen plasma flame flow power and temperature-control circuit power power-supply at last, after workpiece is as cold as room temperature with stove, take out workpiece, obtain copper base pattern structure interface diamond coatings.
9. the preparation method of a kind of copper base pattern structure according to claim 8 interface diamond coatings is characterized in that: the described CVD diamond deposition of steps A system is that heated filament CVD system, microwave CVD system or direct current plasma spray the CVD system.
10. a kind of copper base pattern structure according to claim 1 interface diamond coatings is applied to prepare microelectronics heat sink material or electronic equipment dissipating heat material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6248400B1 (en) * | 1993-08-12 | 2001-06-19 | Fujitsu Limited | Vapor phase diamond synthesis method |
| CN101070461A (en) * | 2007-05-18 | 2007-11-14 | 中南大学 | Super-high heat-conductive diamond-copper composite package material and production method |
| US20090256263A1 (en) * | 2008-04-09 | 2009-10-15 | International Business Machines Corporation | Structure and method for hybrid tungsten copper metal contact |
| CN101775587A (en) * | 2010-01-12 | 2010-07-14 | 中国科学院宁波材料技术与工程研究所 | Micro-drill for copper alloy processing and preparation method thereof |
-
2010
- 2010-08-31 CN CN2010102706603A patent/CN101935837B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6248400B1 (en) * | 1993-08-12 | 2001-06-19 | Fujitsu Limited | Vapor phase diamond synthesis method |
| CN101070461A (en) * | 2007-05-18 | 2007-11-14 | 中南大学 | Super-high heat-conductive diamond-copper composite package material and production method |
| US20090256263A1 (en) * | 2008-04-09 | 2009-10-15 | International Business Machines Corporation | Structure and method for hybrid tungsten copper metal contact |
| CN101775587A (en) * | 2010-01-12 | 2010-07-14 | 中国科学院宁波材料技术与工程研究所 | Micro-drill for copper alloy processing and preparation method thereof |
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| CN102337514A (en) * | 2011-09-22 | 2012-02-01 | 中国航天科技集团公司第五研究院第五一○研究所 | Method for growing strong-adhesiveness diamond thin film on copper substrate through diamond embedding method |
| CN102634793A (en) * | 2012-04-20 | 2012-08-15 | 郑州大学 | Flexible substrate nanometer diamond thin film as well as preparation method and application thereof |
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| CN104878447A (en) * | 2015-06-04 | 2015-09-02 | 哈尔滨工业大学 | Seed crystal-substrate in-situ connection method for homoepitaxial-growth monocrystalline diamond |
| CN104972189A (en) * | 2015-07-30 | 2015-10-14 | 哈尔滨工业大学 | Vacuum brazing method for seed crystal substrate for homoepitaxial growing of monocrystal diamond |
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