Microwave plasma reactors and substrates for synthetic diamond manufacture

• US 8,859,058 B2
• Filed: 12/14/2011
• Issued: 10/14/2014
• Est. Priority Date: 12/23/2010
• Status: Active Grant

• Current Assignee: Element Six (Holdings) Ltd. (Anglo American PLC)
• Original Assignee: Element Six (Holdings) Ltd. (Anglo American PLC)
• Inventors: Inglis, Paul Nicolas, Scarsbrook, Geoffrey Alan, Mollart, Timothy Peter, Pickles, Charles Simon James, Coe, Steven Edward, Dodson, Joseph Michael, Cullen, Alexander Lamb, Brandon, John Robert, Wort, Christopher John Howard, Dodge, Carlton Nigel
• Primary Examiner(s): TUROCY, DAVID P
• Application Number:
  US13/994,813
• Publication Number:
  US 20140234556A1
• Time in Patent Office: 1,035 Days
• Field of Search: 427/574
• US Class Current: 427/575
• CPC Class Codes: C01B 32/26 Preparation by using ultra-high pressure B01J3/06; by crystal growth C30B29/04
• CPC Class Codes: C23C 16/274 using microwave discharges
• CPC Class Codes: C23C 16/4586 Elements in the interior of the support, e.g. electrodes, heating or cooling devices
• CPC Class Codes: C23C 16/511 using microwave discharges
• CPC Class Codes: C23C 16/52 Controlling or regulating the coating process C23C16/45557, C23C16/279 take precedence
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: C30B 25/105 by irradiation or electric discharge
• CPC Class Codes: C30B 29/04 Diamond
• CPC Class Codes: H01J 37/32192 Microwave generated discharge H01J37/32357, H01J37/32366, H01J37/32394, H01J37/32403 take precedence
• CPC Class Codes: H01J 37/32284 Means for controlling or selecting resonance mode
• CPC Class Codes: Y10T 428/12993 Surface feature [e.g., rough, mirror]

Abstract

A microwave plasma reactor for manufacturing synthetic diamond material via chemical vapor deposition, the microwave plasma reactor comprising: a microwave generator configured to generate microwaves at a frequency f; a plasma chamber comprising a base, a top plate, and a side wall extending from said base to said top plate defining a resonance cavity for supporting a microwave resonance mode between the base and the top plate; a microwave coupling configuration for feeding microwaves from the microwave generator into the plasma chamber; a gas flow system for feeding process gases into the plasma chamber and removing them therefrom; a substrate holder disposed in the plasma chamber and comprising a supporting surface for supporting a substrate; and a substrate disposed on the supporting surface, the substrate having a growth surface on which the synthetic diamond material is to be deposited in use, wherein the substrate dimensions and location within the resonance cavity are selected to generate a localized axisymmetric E_z electric field profile across the growth surface in use, the localized axisymmetric E_z electric field profile comprising a substantially flat central portion bound by a ring of higher electric field, the substantially flat central portion extending over at least 60% of an area of the growth surface of the substrate and having an E_z electric field variation of no more than ±10% of a central E_z electric field strength, the ring of higher electric field being disposed around the central portion and having a peak E_z electric field strength in a range 10% to 50% higher than the central E_z electric field strength.

Claims

1. A method of manufacturing synthetic diamond material via chemical vapour deposition, the method comprising:

providing a microwave plasma reactor comprising;

a microwave generator configured to generate microwaves at a frequency f;

a plasma chamber comprising a base, a top plate, and a side wall extending from said base to said top plate defining a resonance cavity for supporting a microwave resonance mode between the base and the top plate;

a microwave coupling configuration for feeding microwaves from the microwave generator into the plasma chamber;

a gas flow system for feeding process gases into the plasma chamber and removing them therefrom; and

a substrate holder disposed in the plasma chamber and comprising a supporting surface for supporting a substrate;

locating a substrate over the supporting surface of the substrate holder, the substrate having a growth surface on which the synthetic diamond material is to be deposited,

feeding process gases into the plasma chamber; and

feeding microwaves into the plasma chamber to form a plasma over the growth surface of the substrate and grow synthetic diamond material on the growth surface of the substrate,

wherein the substrate dimensions and location within the resonance cavity are selected to generate a localized axisymmetric E_z electric field profile across the growth surface in use, the localized axisymmetric E_z electric field profile comprising a substantially flat central portion bound by a ring of higher electric field, the substantially flat central portion extending over at least 60% of an area of the growth surface of the substrate and having an E_z electric field variation of no more than ±

10% of a central E_z electric field strength, the ring of higher electric field being disposed around the central portion and having a peak E_z electric field strength in a range 10% to 50% higher than the central E_z electric field strength.

2. The method of claim 1, wherein the substantially flat central portion of the localized axisymmetric E_z electric field profile has an electric field variation of no more than ±

8%, 6%, 5%, 4%, 3%, 2%, or 1% of the central E_z electric field strength.

3. The method of claim 1, wherein the ring of higher electric field has a peak E_z electric field strength in a range 10% to 40%, 15% to 30%, or 15% to 25% higher than the central E_z electric field strength.

4. The method of claim 1, wherein the localized axisymmetric E_z electric field profile is calculated at a height above the growth surface of the substrate of:

4 mm, 6 mm, or 8 mm for a microwave frequency f in a range 400 MHz to 500 MHz;

2 mm, 3 mm, or 4 mm for a microwave frequency f in a range 800 MHz to 1000 MHz;

or

0.7 mm, 1.0 mm, or 1.5 mm for a microwave frequency f in a range 2300 MHz to 2600 MHz.

5. The method of claim 1,

wherein a ratio of substrate diameter/height of the growth surface of the substrate above the base of the plasma chamber is in a range 10 to 14, 11 to 13.5, or 11.0 to 12.5.

6. The method of claim 5, wherein the height of the growth surface of the substrate above the base of the plasma chamber is in the range:

10 mm to 30 mm or 14 mm to 27 mm for a microwave frequency f in the range 400 to 500 MHz;

5 mm to 15 mm or 7 mm to 13 mm for a microwave frequency f in the range 800 to 1000 MHz;

or

2.0 mm to 5.5 mm or 2.5 mm to 5.0 mm for a microwave frequency f in the range 2300 to 2600 MHz.

7. The method of claim 5, wherein the microwave frequency f in the range 400 MHz to 500 MHz and the substrate diameter and the height of the growth surface of the substrate within the resonance cavity are selected such that:

if the substrate diameter is in the range 180 mm to 230 mm, the height of the growth surface is in the range 14 mm to 20 mm;

if the substrate diameter is in the range 230 mm to 270 mm, the height of the growth surface may is in the range 20 mm to 24 mm;

or

if the substrate diameter is in the range 270 mm to 310 mm, the height of the growth surface is in the range 22 mm to 27 mm.

8. The method of claim 5, wherein the microwave frequency f in the range 800 MHz to 1000 MHz and the substrate diameter and the height of the growth surface of the substrate within the resonance cavity are selected such that:

if the substrate diameter is in the range 90 mm to 110 mm, the height of the growth surface is in the range 7 mm to 10 mm;

if the substrate diameter is in the range 110 mm to 130 mm, the height of the growth surface may is in the range 9.5 mm to 11.5 mm;

or

if the substrate diameter is in the range 130 mm to 150 mm, the height of the growth surface is in the range 11 mm to 13 mm.

9. The method of claim 5, wherein the microwave frequency f in the range 2300 MHz to 2600 MHz and the substrate diameter and the height of the growth surface of the substrate within the resonance cavity are selected such that:

if the substrate diameter is in the range 30 mm to 40 mm, the height of the growth surface is in the range 2.5 mm to 3.7 mm;

if the substrate diameter is in the range 40 mm to 48 mm, the height of the growth surface may is in the range 3.5 mm to 4.2 mm;

or

if the substrate diameter is in the range 48 mm to 55 mm, the height of the growth surface is in the range 4.0 mm to 4.8 mm.

10. The method of claim 1, wherein the substrate diameter is in the range:

165 mm to 415 mm, 185 mm to 375 mm, 205 mm to 375 mm, 205 mm to 330 mm, or 240 mm to 330 mm for a microwave frequency f in the range 400 to 500 MHz;

80 mm to 200 mm, 90 mm to 180 mm, 100 mm to 180 mm, 100 mm to 160, or 115 mm to 160 mm for a microwave frequency f in the range 800 to 1000 MHz;

or

30 mm to 75 mm, 33 mm to 65 mm, 37 mm to 65 mm, 37 mm to 58 mm, or 42 mm to 58 mm for a microwave frequency f in the range 2300 to 2600 MHz.

11. The method of claim 1, wherein a ratio of a resonance cavity diameter/substrate diameter is in the range 1.5 to 5, 2.0 to 4.5, or 2.5 to 4.0, wherein the resonance cavity diameter is measured at a height less than 50%, 40%, 30%, or 20% of a height of the resonance cavity.

12. The method of claim 11, wherein the resonance cavity diameter is measured at a height of the growth surface of the substrate.

13. The method of claim 1, further comprising:

taking at least two temperature measurements using one or more temperature measurement devices, including one or more measurements in a central region of the growth surface of the substrate and one or more measurements in a peripheral region of the growth surface; and

controlling a temperature difference between the central region and the peripheral region of the growth surface of the substrate during CVD diamond growth thereon based on the at least two temperature measurements using a substrate temperature control system.

14. The method of claim 13, wherein the substrate temperature control system is used to control the temperature of the growth surface of the substrate during CVD diamond growth thereon to fulfil the condition:

5°

C.<

T_c−

T_e<

120°

C.;

10°

C.<

T_c−

T_e<

100°

C.;

10°

C.<

T_c−

T_e<

80°

C.;

20°

C.<

T_c−

T_e<

80°

C.;

or 20°

C.<

T_c−

T_e<

60°

C., where T_c is a temperature in the central region of the growth surface and T_e is a temperature in the peripheral region of the growth surface.

15. The method of claim 13, wherein the central region of the growth surface has an outer diameter no greater than 50%, 40%, 30%, 20%, or 10% of the diameter of the growth surface and the peripheral region of the growth surface has an inner diameter greater than 50%, 60%, 70%, 80%, 90% or 95% of the diameter of the growth surface.

16. The method of claim 1, wherein the substrate is disposed over the supporting surface of the substrate holder and spaced apart by spacer elements to form a gas gap having a height h between the supporting surface of the substrate holder and a rear surface of the substrate, and the microwave plasma reactor further comprising a gas supply system for supplying gas to said gas gap, the spacer elements being configured to define a central gas gap cavity under the substrate in which gas from the gas supply system can pool.

17. The method of to claim 16, wherein the height h of the gas gap is in the range 25 μ

m to 2000 μ

m, 50 μ

m to 1000 μ

m, 100 μ

m to 750 μ

m, 500 μ

m to 750 μ

m, 600 μ

m to 650 μ

m, 100 μ

m to 300 μ

m, or 150 μ

m to 250 μ

m.

18. The method of claim 16, wherein the height h of the gas gap varies by no more than 200 μ

m, 150 μ

m 100 μ

m, 80 μ

m, 60 μ

m, 40 μ

m, 20 μ

m, 10 μ

m, or 5 μ

m across at least a central region of the substrate having a centred diameter equal to or greater than 60%, 70%, 80%, 90%, 95%, or 99% of a total diameter of the substrate.

19. A method according to claim 16, wherein the gas gap has a central region with a first gas gap height and a peripheral region with a second gas gap height, the first gas gap height being larger than the second gas gap height.