CN110184653A - A method of improving large size single crystal diamond seam quality - Google Patents
A method of improving large size single crystal diamond seam quality Download PDFInfo
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- CN110184653A CN110184653A CN201910483756.9A CN201910483756A CN110184653A CN 110184653 A CN110184653 A CN 110184653A CN 201910483756 A CN201910483756 A CN 201910483756A CN 110184653 A CN110184653 A CN 110184653A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/20—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer
- C30B25/205—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer the substrate being of insulating material
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/04—Diamond
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Abstract
A method of large size single crystal diamond seam quality is improved, single crystal diamond material field is belonged to.After two panels single-crystal diamond is polished directly simultaneously, low-dislocation-density, high quality splicing seam cutting processing are realized after surface carries out different form cutting processing using laser ablation, electron beam lithography, ICP lithographic technique or focused ion beam bombardment method, then two single-crystal diamonds are subjected to splicing growth under microwave plasma conditions, two panels single-crystal diamond is spliced together again by horizontal extension finally, obtains the high quality large area single-crystal diamond of no splicing seams.The shielding to microwave plasma may be implemented in different micro groove structures, to optimize the ratio of transverse and longitudinal growth rate, and then effectively inhibit dislocation defects caused by horizontal extension, it avoids that polycrystallization phenomenon occurs in CVD growth layer or dislocation continues the low mass region to form high dislocation density, realizes the raising of diamond seam quality.
Description
Technical field
The invention belongs to single crystal diamond material growing technology fields；Relate to a kind of utilization Mosaic face periodicity quarter
The method that slot technology improves large size single crystal diamond seam quality, feature are passed through for not ipsilateral oriented single crystal diamond
It realizes that low-dislocation-density, high quality splice seam after stitching position carries out different form cutting processing, finally realizes large area
The splicing of diamond is grown.
Technical background
Single-crystal diamond as a kind of wide bandgap semiconductor, heat, power, light, in terms of all there is excellent performance.Such as
With thermal conductivity is high, heat dissipation effect is significant at high temperature；Diamond is most hard natural materials, is widely used in cutter, grinding tool etc.
Coating material；All there is high transmitance to infrared entire wave band diamond from ultraviolet；In addition diamond has wider band
Gap (5.5eV), high carrier mobility (especially hole mobility is more much higher than single crystalline Si, GaAs), low-k (5.7)
Deng being known as the ultimate semiconductor material with wide forbidden band in high-frequency high-power and high-temperature pressure-proof field.However natural diamond and height
The artificial synthesized single-crystal diamond size of warm high pressure is smaller, and quality is generally difficult to meet electronic device applications.Microwave etc. from
Daughter chemical vapour deposition technique can be realized the growth of large-size high-quality single-crystal diamond, be expected to prepare electronic device use
Single-crystal diamond chip.But the preparation of large size single crystal diamond is mainly still based on isoepitaxial growth at present, by growth machine
The influence of system, growth rate is more slow, so the single-crystal diamond size needs of preparation are strongly depend on natural or high temperature height
The size of artificial synthesized single-crystal diamond substrate is pressed, and during the growth process, due to different crystal face competitive growths, side surface exists
The influence of the defects of higher defect concentration and substrate dislocation can be generated in growth course heredity, is unable to satisfy electronic device
Demand of the industry for inch grade chip.Scholars start to explore the preparation of large-size high-quality single-crystal diamond thus, at present
Especially the size that single-crystal diamond is obtained in a manner of splicing growth is maximum, up to 2 inches of (Appl.Phys.Lett.104 (2014)
102).However splicing the greatest problem that growing method faces is that seam crossing has microcosmic difference in height and gap, is given birth in splicing
Since interface is obviously difficult to realize be seamlessly connected in length, the large area single-crystal diamond seam crossing for causing splicing to grow is easy to appear
The defects of polycrystallization, dislocation density is high, quality and the single-crystal diamond quality difference of substrate surface epitaxial growth are larger, it is difficult at
For the large-size high-quality single-crystal diamond chip of real meaning, it is unable to satisfy the preparation of large scale electronics grade diamond.
The diamond seeds for being oriented to (111) are arranged in the Si lining for having already patterned etching processing by initial Geis M W etc.
On bottom, continuous diamond thin is gone out by epitaxial growth, but there are low-angle boundary (Appl.Phys.Lett.58 in film
(1991)2485).Mosaic technology has significant progress to be Meguro K et al. to be prepared for thick outer of 1mm by CVD method
Prolong diamond thin, but there are still more serious dislocation (New.Diam.Fron.12 (2002) 125) between initial substrate.
It is found after Muchnikov AB et al. 4 pieces of natural diamond direct splicings of use, the region meeting " heredity " of the CVD layer of epitaxial growth
The crystalline orientation of respective substrate, which results in stress always to concentrate on splicing regions, dislocation, region existing for impurity
(Jour.Crys.Grow.442(2016)62).In order to solve the problems, such as that splicing seams are ropy, Yamada H et al. use clone,
Lift-off technology, the substrate by combining same orientation are prepared for 2 inches of large size single crystal diamond
(Appl.Phys.Lett.104(2014)102).But the more cloning procedure being related to of the method step is complicated, and epitaxial layer material
Radiation defect caused by the easily hereditary ion implanting of material.
Some patents about joining method are also reported at present, and two single-crystal surfaces are cut by CN108754600A proposition
Spliced on inclined-plane parallel to each other；CN108977880A describes a kind of side for intersecting splicing growing large-area single-crystal diamond
Method, two pieces of diamond single crystal microstructures of growth connection since crosspoint；Patent CN108677246A proposes a kind of bridging
Splice the method for growing large-area single-crystal diamond, two monocrystalline grow bridge like coupling part in seam crossing, and it is raw to continue extension
Length obtains complete large area single crystal diamond layer.Although the splicing growth of two seed crystals may be implemented in these methods, but still
It is connected with each other based on two interface longitudinal growths, is increased with growth thickness, coupling part is gradually expanded, and ultimately forms splicing
Body, interface location defect concentration is high, larger with two seed crystal Epitaxial Growth of Diamond layer quality differences.
Summary of the invention
Key technical problem to be solved by this invention is to change general joining method, is solved caused by seed crystal direct splicing
Stitching portion crack is big, the ropy problem of splicing regions.Using Mosaic face periodicity cutting technology, optimize transverse and longitudinal growth rate
Ratio, and then effectively inhibit dislocation defects caused by horizontal extension, realize the raising of diamond seam quality, it is final to realize height
Quality large area single crystal diamond film.
A method of improving large size single crystal diamond seam quality, it is characterised in that: two panels single-crystal diamond is same
When be polished directly after, surface using laser ablation, electron beam lithography, ICP lithographic technique or focused ion beam Hong
It the methods of hits after carrying out different form cutting processing and realizes low-dislocation-density, high quality splicing seam cutting processing, then by two
A single-crystal diamond carries out splicing growth under microwave plasma conditions, finally again by two panels single-crystal diamond by lateral out
Prolong and be spliced together, obtains the high quality large area single-crystal diamond of no splicing seams.
A kind of method improving large size single crystal diamond seam quality as described above, specific process step are as follows:
(1) take two block sizes in 3~8mm single-crystal diamond, to its surface, side is ground simultaneously, is adopted respectively
1~2h is ground with the diamond lap powder of W40, W20, W10, W5, final two pieces of single-crystal diamond abradant surfaces are flat and smooth and have
There is identical thickness；
(2) to after grinding surface and side carry out mechanical polishing processing, so that sample is polished to difference in height at 10 μm
Within, surface roughness is lower than 1nm；
(3) to the sample pickling after polishing, sample is cleaned by ultrasonic later；
(4) laser ablation microflute is focused on LASER SPECKLE using laser at the position of required cutting, and laser function is set
2~5KW of rate, 1~10mm/s of laser step carry out laser grooving according to the pattern dimension set；
(5) sample after laser treatment is cleaned by ultrasonic, it is right under hydrogen or hydrogen/oxygen condition of plasma
Substrate surface carry out plasma etching, after using acetone, EtOH Sonicate clean 10~30min, remove laser ablation carbon
Change part；
(6) by cutting, treated that single-crystal diamond substrate is put into the chamber of microwave plasma device, is passed through hydrogen
Gas or hydrogen/oxygen carry out plasma clean to single-crystal diamond；Using microwave plasma CVD (MPCVD)
Method grows to realize that large-size high-quality single-crystal diamond splices, and after growth, takes out spliced single-crystal diamond, obtains
Obtain large-size high-quality single-crystal diamond.
Further, polishing machine design parameter used in step (2) are as follows: load 200~800,10~30min of time；By two
Block seed crystal is sticked on the same workpiece planarization, so that two seed crystals can polish under identical process conditions, ensure that two seed crystals are thrown
Height and roughness having the same after light；When polishing, low load is first used, is polished at a slow speed, then at a slow speed by top load
Polishing finally achievees the purpose that essence throwing using low load fast polishing.
Further, sulfuric acid and nitric acid that pickling described in step (3) is 5:1 using volume ratio, pickling time 30
~60min；10~30min is respectively first cleaned by ultrasonic to sample with acetone, again with dehydrated alcohol later.
Further, step (4) the laser ablation microflute, concrete scheme is:
1) by two pieces of sides be (100) orientation single-crystal diamond side assembling after cutting handle, the microflute at splicing seams
For single rectangle micro-groove, if rectangle micro-groove width is W1, length W2, depth of mini longitudinal channels d, then rectangle micro-groove length W2 should be with splicing
The length of sample is consistent, and the size of width and depth of mini longitudinal channels should meet following relationship: W1/d=0.1~20；
2) is the single-crystal diamond of (100) orientation similarly for two pieces of sides, when production is parallel to the periodicity of splicing seams
When microflute, if rectangle micro-groove width is W1, length W2, rectangle micro-groove spacing is W3, depth of mini longitudinal channels d, then rectangle micro-groove length
W2 should be consistent with the splicing length of sample, rectangle micro-groove spacing W3=10~500 μm, the ruler of rectangle micro-groove width and depth of mini longitudinal channels
It is very little to meet following relationship: W1/d=0.1~20；
3) is the single-crystal diamond of (110) orientation for side, needs to make across splicing seams and at 45 ° with splicing seams
Microflute；If rectangular recess width is W1, length W2, rectangular recess spacing is W3, depth of groove d, rectangular recess spacing W3
=10~500 μm, rectangular recess length and width should meet following relationship: W2/W1=2~20, rectangular recess width and recessed
The size of groove depth should meet following relationship: W1/d=0.1~20.
Further, step (6) MPCVD method are as follows: be passed through total gas volume 2~
10% methane, growth power are selected as 2000~3800W, 15~25KPa of pressure, and growth temperature is controlled at 700~1000 DEG C,
Growth time is 50~200h.
Large-size high-quality single crystal diamond is realized using microwave plasma enhanced chemical vapor deposition (MPCVD) method
Stone splicing growth, it is advantageous that equipment dependability is strong, job stability is strong, control is accurate etc..
The method of cutting can not only use laser ablation microflute, can also etch skill using electron beam lithography, ICP
The methods of art and focused ion beam bombardment are realized.
Splicing growth for diamond single crystal material, due to the difference of different high preferred orientations, side during growth
Surface can generate higher defect concentration, and lattice misfit and stress is caused to be concentrated, and then inevitably to generate polycrystalline in stitching portion
Phase causes monocrystalline phase surface product to reduce, to seriously limit the increase of single-crystal diamond size.The present invention passes through in monocrystalline gold
The various forms of cutting processing in hard rock stitching portion, optimize the ratio of transverse and longitudinal growth rate, and then effectively horizontal extension is inhibited to be produced
Raw dislocation defects.
Beneficial effect possessed by the present invention and the prior art is:
(1) in microwave plasma, the enhancing of microcell local plasma is can be achieved in the presence of microflute, forms plasma
Local eddy currents, so that uniformity of temperature profile in region, surface epitaxial layer homogenizes distribution, can be realized in microwave plasma ring
Under border in slot Epitaxial Growth of Diamond the best growing condition, realize high-quality growth.
(2) reactant gas molecules cohesion microcell can be achieved in the presence of microflute, accelerates so that cross growth is opposite, was growing
It can control the horizontal and vertical growth rate ratio of single-crystal diamond in journey, realize transversal epitaxial growth and be seamlessly connected.
(3) presence of microflute makes transversal epitaxial growth direction vertical with dislocation direction, can effectively inhibit substrate microflute
The dislocation heredity of bottom, to reduce the dislocation density of diamond growth layer, avoids CVD growth layer from polycrystallization phenomenon or position occur
Mistake continues the low mass region for forming high dislocation density, to improve the crystal quality of diamond.
Detailed description of the invention
In order to illustrate more clearly of technical solution of the present invention, brief Jie will be to attached drawing used in embodiment below
It continues.Following attached drawing is only brief introduction of the invention.
Fig. 1 is single-crystal diamond substrate A and single-crystal diamond in the method for general splicing growing large-size single-crystal diamond
Top view of the substrate B when splicing original state；
Fig. 2 is single-crystal diamond substrate A and single-crystal diamond in the method for general splicing growing large-size single-crystal diamond
Main view of the substrate B when splicing original state；
Fig. 3 be the present invention it is a kind of improve large size single crystal diamond seam quality method in single-crystal diamond substrate A and
When the single-crystal diamond side substrate B is that (100) are orientated, top view when splicing original state after single microflute is carved in stitching portion；
Fig. 4 be the present invention it is a kind of improve large size single crystal diamond seam quality method in single-crystal diamond substrate A and
When the single-crystal diamond side substrate B is that (100) are orientated, main view when splicing original state after single microflute is carved in stitching portion；
Fig. 5 be the present invention it is a kind of improve large size single crystal diamond seam quality method in single-crystal diamond substrate A and
It is the periodical microflute for being parallel to splicing seams that the single-crystal diamond side substrate B, which is orientated when institute micro-grooving for (100), splices initial shape
Top view when state；
Fig. 6 be the present invention it is a kind of improve large size single crystal diamond seam quality method in single-crystal diamond substrate A and
It is the periodical microflute for being parallel to splicing seams that the single-crystal diamond side substrate B, which is orientated when institute micro-grooving for (100), splices initial shape
Main view when state；
Fig. 7 be the present invention it is a kind of improve large size single crystal diamond seam quality method in single-crystal diamond substrate A and
When the single-crystal diamond side substrate B is that (110) are orientated, institute's micro-grooving is across splicing seams and micro- with splicing seams periodicity at 45 °
Slot splices top view when original state；
Fig. 8 is the main view after single-crystal diamond substrate A of the present invention and single-crystal diamond substrate B splicing growth；W1. cutting
Width；W2. cutting length；W3. cutting spacing；D. groove depth；
In all figures: 1. single-crystal diamond substrate A；2. single-crystal diamond substrate B；3. big after the completion of splicing in the present invention
Area single crystal diamond film layer.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
The embodiment of invention, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, belongs to protection scope of the present invention.
The present invention provides a kind of methods for improving large size single crystal diamond seam quality, as shown in the picture, by two panels
The processing of single-crystal diamond surface groove, institute's micro-grooving is single rectangle micro-groove or periodic rectangular microflute, then using microwave etc.
Gas ions assistant chemical vapor deposition (MPCVD) method grows to realize that large-size high-quality single-crystal diamond splices.
Embodiment 1
It is had the following steps using the method for laser grooving splicing growth of large size high quality single-crystal diamond:
Two pieces of sides are selected to be oriented to the single-crystal diamond of (100), having a size of 4 × 4 × 1mm3With 4 × 4 × 1mm3, simultaneously
It is set on grinding work-piece with paraffin, their surfaces and splicing side is ground, it is W40 that granularity, which is respectively adopted,
The diamond lap powder of W20, W10, W5 grind 1h, keep two pieces of single-crystal diamond abradant surfaces flat and smooth and thickness having the same
Degree.To after grinding surface and side carry out mechanical polishing processing, first use load 200, time 5min, then load is increased to
600,10min is polished, load 400 is finally used, polishes 10min, difference in height is 5 μm after polishing, and surface roughness is
0.3nm；Using the volume ratio of sulfuric acid and nitric acid 5:1 to the sample pickling 30min after polishing, acetone, anhydrous second are used respectively later
Alcohol is cleaned by ultrasonic 10min to sample；Cutting processing is carried out using laser according to design microflute size, wherein microflute is single square
Shape microflute W1=50 μm of size, W2=4000 μm, d=10 μm, meets following relationship: W1/d=0.1 as shown in Figures 3 and 4
~20.LASER SPECKLE is focused at the position of required cutting, set laser power 2KW, laser step 5mm/s, according to design
Pattern dimension carry out laser grooving；Sample after laser treatment is cleaned by ultrasonic, hydrogen or hydrogen/oxygen etc. from
Plasma etching is carried out to substrate surface under the conditions of daughter, is cleaned by ultrasonic respectively after etching using acetone, ethyl alcohol
10min removes laser ablation carbonized part；By cutting, treated that single-crystal diamond substrate is put into microwave plasma device
Chamber in, be passed through 300sccm hydrogen, 2% methane, growth power is selected as 2800W, pressure 17KPa, growth temperature control
At 750 DEG C or so, single-crystal diamond is carried out under this technique and splices growth test, growth time 50h；After growth, take
Spliced single-crystal diamond out, obtains 4.5 × 8.5 × 1.2mm3The single-crystal diamond of large-size high-quality splicing seams.
Embodiment 2
It is had the following steps using the method for laser grooving splicing growth of large size high quality single-crystal diamond:
Two pieces of sides are selected to be oriented to the single-crystal diamond of (100), having a size of 8 × 8 × 1mm3With 8 × 8 × 1mm3, simultaneously
It is set on grinding work-piece with paraffin, their surfaces and splicing side is ground, it is W40 that granularity, which is respectively adopted,
The diamond lap powder of W20, W10, W5 grind 1h, keep two pieces of single-crystal diamond abradant surfaces flat and smooth and thickness having the same
Degree.To after grinding surface and side carry out mechanical polishing processing, first use load 400, time 5min, then load is increased to
600,10min is polished, load 400 is finally used, polishes 10min, difference in height is 8 μm after polishing, and surface roughness is
0.6nm；Using the volume ratio of sulfuric acid and nitric acid 5:1 to the sample pickling 60min after polishing, acetone, anhydrous second are used respectively later
Alcohol is cleaned by ultrasonic 10min to sample；Cutting processing is carried out using laser according to design microflute size, production is parallel to splicing seams
Periodic rectangular microflute, it is W2=8000 μm, W3=500 μm, d=100 μm, full as it can be seen in figures 5 and 6, W1=200 μm of size
Sufficient following relationship: W1/d=0.1~20.LASER SPECKLE is focused at the position of required cutting, sets laser power 3KW,
Laser step 10mm/s, the pattern dimension according to design carry out laser grooving；Sample after laser treatment is cleaned by ultrasonic,
Plasma etching is carried out to substrate surface under hydrogen or hydrogen/oxygen condition of plasma, utilizes third after etching
Ketone, ethyl alcohol are cleaned by ultrasonic 10min respectively, remove laser ablation carbonized part；By treated the single-crystal diamond substrate of cutting
It is put into the chamber of microwave plasma device, is passed through 300sccm hydrogen, 5% methane, growth power is selected as 3200W, pressure
Power 20KPa, growth temperature are controlled at 850 DEG C or so, and single-crystal diamond is carried out under this technique and splices growth test, growth time
For 150h；After growth, spliced single-crystal diamond is taken out, 8.5 × 16.5 × 1.6mm is obtained3Large-size high-quality
The single-crystal diamond of splicing seams.
Embodiment 3
It is had the following steps using the method for laser grooving splicing growth of large size high quality single-crystal diamond:
Two pieces of sides are selected to be oriented to the single-crystal diamond of (110), having a size of 4 × 4 × 1mm3With 4 × 4 × 1mm3, simultaneously
It is set on grinding work-piece with paraffin, their surfaces and splicing side is ground, it is W40 that granularity, which is respectively adopted,
The diamond lap powder of W20, W10, W5 grind 2h, keep two pieces of single-crystal diamond abradant surfaces flat and smooth and thickness having the same
Degree.To after grinding surface and side carry out mechanical polishing processing, first use load 400, time 5min, then load is increased to
800,10min is polished, load 400 is finally used, polishes 10min, difference in height is 9 μm after polishing, and surface roughness is 1nm；
Using the volume ratio of sulfuric acid and nitric acid 5:1 to the sample pickling 60min after polishing, acetone is used respectively later, dehydrated alcohol is to examination
Sample is cleaned by ultrasonic 10min；According to design microflute size using laser carry out cutting processing, production across splicing seams and with splicing
Rectangle micro-groove at 45 ° is stitched, as shown in fig. 7, W1=20 μm of size, W2=50 μm, W3=100 μm, d=50 μm, meet following
Relational expression: W1/d=0.1~20.LASER SPECKLE is focused at the position of required cutting, sets laser power 5KW, laser step
Long 10mm/s, the pattern dimension according to design carry out laser grooving；Sample after laser treatment is cleaned by ultrasonic, in hydrogen
Or plasma etching is carried out to substrate surface under hydrogen/oxygen condition of plasma, acetone, ethyl alcohol are utilized after etching
It is cleaned by ultrasonic 10min respectively, removes laser ablation carbonized part；By cutting, treated that single-crystal diamond substrate is put into microwave
In the chamber of plasma apparatus, it is passed through 300sccm hydrogen, 10% methane, growth power is selected as 3500W, pressure
22KPa, growth temperature are controlled at 950 DEG C or so, and single-crystal diamond is carried out under this technique and splices growth test, growth time is
200h；After growth, spliced single-crystal diamond is taken out, 4.6 × 8.6 × 1.7mm is obtained3Large-size high-quality splicing
The single-crystal diamond of seam.
The above, part specific embodiment only of the invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (6)
1. a kind of method for improving large size single crystal diamond seam quality, it is characterised in that: simultaneously by two panels single-crystal diamond
After being polished directly, on surface using laser ablation, electron beam lithography, ICP lithographic technique or focused ion beam bombardment
Method realizes low-dislocation-density, high quality splicing seam cutting processing after carrying out different form cutting processing, then by two lists
Diamond carries out splicing growth under microwave plasma conditions, finally again spells two panels single-crystal diamond by horizontal extension
It is connected to the high quality large area single-crystal diamond for obtaining no splicing seams together.
2. a kind of method for improving large size single crystal diamond seam quality as described in claim 1, which is characterized in that specific work
Skill step are as follows:
(1) take two block sizes in 3~8mm single-crystal diamond, to its surface, side is ground simultaneously, is respectively adopted
The diamond lap powder of W40, W20, W10, W5 grind 1~2h, and final two pieces of single-crystal diamond abradant surfaces are flat and smooth and have
Identical thickness；
(2) to after grinding surface and side carry out mechanical polishing processing, so that sample is polished to difference in height within 10 μm,
Surface roughness is lower than 1nm；
(3) to the sample pickling after polishing, sample is cleaned by ultrasonic later；
(4) laser ablation microflute is focused on LASER SPECKLE using laser at the position of required cutting, and laser power 2 is set
~5KW, 1~10mm/s of laser step carry out laser grooving according to the pattern dimension set；
(5) sample after laser treatment is cleaned by ultrasonic, to substrate under hydrogen or hydrogen/oxygen condition of plasma
Surface carry out plasma etching, after using acetone, EtOH Sonicate clean 10~30min, remove laser ablation carbonization portion
Point；
(6) by cutting, treated that single-crystal diamond substrate is put into the chamber of microwave plasma device, be passed through hydrogen or
Hydrogen/oxygen carries out plasma clean to single-crystal diamond；Using microwave plasma CVD (MPCVD) method
It is grown to realize that large-size high-quality single-crystal diamond splices, after growth, takes out spliced single-crystal diamond, obtained big
Size high quality single crystal diamond.
3. improving the method for large size single crystal diamond seam quality as claimed in claim 2, it is characterised in that step (2) is used
Polishing machine design parameter are as follows: load 200~800,10~30min of time；Two pieces of seed crystals are sticked on the same workpiece planarization, are made
Obtaining two seed crystals can polish under identical process conditions, ensure that height and roughness having the same after the polishing of two seed crystals；
When polishing, first use low load, polish at a slow speed, then polished at a slow speed by top load, finally using low load fast polishing come
Achieve the purpose that essence throwing.
4. improving the method for large size single crystal diamond seam quality as claimed in claim 2, it is characterised in that step (3) is described
Pickling using volume ratio be 5:1 sulfuric acid and nitric acid, 30~60min of pickling time；Later first with acetone, again with anhydrous
Ethyl alcohol is respectively cleaned by ultrasonic 10~30min to sample.
5. improving the method for large size single crystal diamond seam quality as claimed in claim 2, it is characterised in that step (4) is described
Laser ablation microflute, concrete scheme are:
1) by two pieces of sides be (100) orientation single-crystal diamond side assembling after cutting handle, microflute is single at splicing seams
A rectangle micro-groove, if rectangle micro-groove width is W1, length W2, depth of mini longitudinal channels d, then rectangle micro-groove length W2 should be with splicing sample
Length it is consistent, the size of width and depth of mini longitudinal channels should meet following relationship: W1/d=0.1~20；
2) is the single-crystal diamond of (100) orientation similarly for two pieces of sides, when production is parallel to the periodical microflutes of splicing seams
When, if rectangle micro-groove width is W1, length W2, rectangle micro-groove spacing is W3, and depth of mini longitudinal channels d, then rectangle micro-groove length W2 is answered
Consistent with the splicing length of sample, the size of rectangle micro-groove spacing W3=10~500 μm, rectangle micro-groove width and depth of mini longitudinal channels is answered
Meet following relationship:
W1/d=0.1~20；
3) is the single-crystal diamond of (110) orientation for side, need to make across splicing seams and at 45 ° micro- of splicing seams
Slot；If rectangular recess width is W1, length W2, rectangular recess spacing is W3, depth of groove d, rectangular recess spacing W3=10
~500 μm, rectangular recess length and width should meet following relationship: W2/W1=2~20, and rectangular recess width and groove are deep
The size of degree should meet following relationship: W1/d=0.1~20.
6. improving the method for large size single crystal diamond seam quality as claimed in claim 2, it is characterised in that step (6) is described
MPCVD method are as follows: be passed through 2~10% methane of total gas volume, growth power is selected as 2000
~3800W, 15~25KPa of pressure, at 700~1000 DEG C, growth time is 50~200h for growth temperature control.
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| CN112030228A (en) * | 2020-09-11 | 2020-12-04 | 哈尔滨工业大学 | Bridging temperature control method for co-growth of multiple MPCVD single crystal diamonds |
| CN112391680A (en) * | 2020-11-16 | 2021-02-23 | 物生生物科技(北京)有限公司 | Splicing growth process for large-size single crystal diamond |
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| CN114959891A (en) * | 2022-03-30 | 2022-08-30 | 上海征世科技股份有限公司 | Single crystal diamond and MPCVD preparation method thereof |
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