Microwave plasma reactors

• US 8,668,962 B2
• Filed: 10/22/2012
• Issued: 03/11/2014
• Est. Priority Date: 06/16/2008
• Status: Active Grant

• Current Assignee: Fraunhofer USA Inc. (Fraunhofer-Institut für Nachrichtentechnik HHI), The Board of Trustees of Michigan State University (Michigan State University)
• Original Assignee: Fraunhofer USA Inc. (Fraunhofer-Institut für Nachrichtentechnik HHI), The Board of Trustees of Michigan State University (Michigan State University)
• Inventors: Asmussen, Jes, Grotjohn, Timothy, Reinhard, Donnie K., Schuelke, Thomas, Yaran, M. Kagan, Hemawan, Kadek W., Becker, Michael, King, David, Gu, Yajun, Lu, Jing
• Primary Examiner(s): Turocy, David
• Application Number:
  US13/657,353
• Publication Number:
  US 20130101730A1
• Time in Patent Office: 505 Days
• Field of Search: 427/569, 427/575, 118/723.MW
• US Class Current: 427/575
• CPC Class Codes: C23C 16/274 using microwave discharges
• CPC Class Codes: C23C 16/279 control of diamond crystallography
• CPC Class Codes: C23C 16/511 using microwave discharges
• CPC Class Codes: C30B 25/105 by irradiation or electric discharge
• CPC Class Codes: C30B 25/16 Controlling or regulating controlling or regulating in general G05
• CPC Class Codes: C30B 29/04 Diamond
• CPC Class Codes: C30B 35/00 Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
• CPC Class Codes: H01J 37/32256 Tuning means
• CPC Class Codes: H05H 1/46 using applied electromagnetic fields, e.g. high frequency or microwave energy H05H1/26 takes precedence

Abstract

New and improved microwave plasma assisted reactors, for example chemical vapor deposition (MPCVD) reactors, are disclosed. The disclosed microwave plasma assisted reactors operate at pressures ranging from about 10 Torr to about 760 Torr. The disclosed microwave plasma assisted reactors include a movable lower sliding short and/or a reduced diameter conductive stage in a coaxial cavity of a plasma chamber. For a particular application, the lower sliding short position and/or the conductive stage diameter can be variably selected such that, relative to conventional reactors, the reactors can be tuned to operate over larger substrate areas, operate at higher pressures, and discharge absorbed power densities with increased diamond synthesis rates (carats per hour) and increased deposition uniformity.

Claims

1. A process for depositing a component on a substrate, the process comprising:

(a) providing a microwave plasma assisted reactor comprising;

(i) a first microwave chamber having a reference plane at a reference axial location Z₀, the first microwave chamber comprising an electromagnetic wave source and extending in an axial direction z>

Z₀;

(ii) a plasma chamber having an outer wall, the plasma chamber extending into the first microwave chamber such that at least a portion of the plasma chamber is located at z>

Z₀ and at least a portion of the plasma chamber is located at z<

Z₀;

(iii) a conductive stage for supporting a substrate holder and having a reference surface extending into the plasma chamber and defining a second microwave chamber in the plasma chamber (i) at z<

Z₀ and (ii) between the plasma chamber outer wall and the conductive stage;

(iv) a conducting short adjustably disposed in the second microwave chamber below Z₀ and in electrical contact with the plasma chamber outer wall and the conductive stage, the axial distance between the conducting short and Z₀ being L2, and the axial distance between the conducting short and the reference surface of the conductive stage being L1; and

(v) a deposition substrate mounted above an upper surface of the conductive stage;

wherein L2 and L1 are capable of adjustment in the reactor by moving the conducting short, such that different microwave modes are produced in the first microwave chamber and in the second microwave chamber during operation of the reactor;

(b) operating the reactor at a pressure ranging from about 10 Torr to about 760 Torr;

(c) adjusting the axial position of the conducting short and optionally the conductive stage of the reactor to optimize at least one of (i) a deposition area of the substrate having a deposition non-uniformity of 15% or less, (ii) a reactor power density, and (iii) a component deposition rate; and

,

(d) depositing a component on the substrate.

2. The process of claim 1, wherein step (c) comprises adjusting the axial position of the conducting short and optionally the conductive stage during the operation of the reactor.

3. The process of claim 1, wherein step (c) comprises adjusting the axial position of the conducting short and the conductive stage.

4. The process of claim 1, wherein the component comprises single-crystal diamond, microcrystalline polycrystalline diamond, or nanocrystalline polycrystalline diamond.

5. The process of claim 4, wherein operating the reactor comprises feeding a source gas comprising hydrogen and methane, wherein the methane is present in the source gas in an amount ranging from about 1 mol. % to about 10 mol. % relative to hydrogen.

6. The process of claim 5, wherein the source gas further comprises nitrogen.

7. The process of claim 1, wherein, during step (b) of operating the reactor, a first electromagnetic mode M₁ is generated in the cylindrical microwave chamber of the reactor, a second electromagnetic mode M₂ is generated in the coaxial microwave chamber of the reactor, and associated evanescent fields are formed in the vicinity of the deposition substrate, thereby forming a hybrid electromagnetic mode M₃ in the plasma chamber and in the vicinity of the deposition substrate.

8. The process of claim 7, wherein M₁ is a TM₀₁₃ electromagnetic mode and M₂ is a TEM₀₀₁ electromagnetic mode.

9. The process of claim 1, further comprising operating the reactor at an excitation frequency of about 2.45 GHz, wherein (i) the operating pressure ranges from about 100 Torr to about 400 Torr and (ii) the reactor power density ranges from about 100 W/cm³ to about 1000 W/cm³.

10. The process of claim 1, further comprising operating the reactor at an excitation frequency of about 2.45 GHz, wherein (i) the operating pressure ranges from about 180 Torr to about 260 Torr and (ii) the reactor power density ranges from about 160 W/cm³ to about 600 W/cm³.

11. The process of claim 1, further comprising operating the reactor at an excitation frequency of about 2.45 GHz, wherein (i) the operating pressure ranges from about 50 Torr to about 150 Torr and (ii) the deposition area of the substrate having a deposition non-uniformity of 15% or less ranges from about 6 cm to about 9 cm in diameter.

12. The process of claim 1, further comprising operating the reactor at an excitation frequency of about 915 MHz, wherein (i) the operating pressure ranges from about 20 Torr to about 100 Torr and (ii) the deposition area of the substrate having a deposition non-uniformity of 15% or less ranges from about 14 cm to about 20 cm in diameter.

13. The process of claim 1, further comprising operating the reactor at an excitation frequency of about 915 MHz, wherein (i) the operating pressure ranges from about 100 Torr to about 160 Torr and (ii) the deposition area of the substrate having a deposition non-uniformity of 15% or less ranges from about 10 cm to about 14 cm in diameter.

14. The process of claim 1, wherein:

(i) the first microwave chamber, the plasma chamber, and the conductive stage have cylindrical cross sections with radii of R1, R2, and R3, respectively; and

(ii) R3/R2 is about 0.5 or less.

15. A process for tuning a microwave plasma assisted reactor, the process comprising:

(a) providing a microwave plasma assisted reactor comprising;

(i) a first microwave chamber having a reference plane at a reference axial location Z₀, the first microwave chamber comprising an electromagnetic wave source and extending in an axial direction z>

Z₀;

(ii) a plasma chamber having an outer wall, the plasma chamber extending into the first microwave chamber such that at least a portion of the plasma chamber is located at z>

Z₀ and at least a portion of the plasma chamber is located at z<

Z₀;

(iii) a conductive stage for supporting a substrate holder and having a reference surface extending into the plasma chamber and defining a second microwave chamber in the plasma chamber (i) at z<

Z₀ and (ii) between the plasma chamber outer wall and the conductive stage;

(iv) a conducting short adjustably disposed in the second microwave chamber below Z₀ and in electrical contact with the plasma chamber outer wall and the conductive stage, the axial distance between the conducting short and Z₀ being L2, and the axial distance between the conducting short and the reference surface of the conductive stage being L1; and

(v) a deposition substrate mounted above an upper surface of the conductive stage;

wherein L2 and L1 are capable of adjustment in the reactor by moving the conducting short, such that different microwave modes are produced in the first microwave chamber and in the second microwave chamber during operation of the reactor;

(b) selecting a plurality of combinations of L1 and L2;

(c) operating the reactor at each of the plurality of combinations of L1 and L2 and at a pressure ranging from about 10 Torr to about 760 Torr to deposit a component on the substrate;

(d) measuring one or more deposition properties resulting from the operation of the reactor at each of the plurality of combinations of L1 and L2; and

,

(e) selecting a set of tuned L1 and L2 values based on the measured deposition properties in part (d).

16. The process of claim 15, wherein the deposition properties comprise one or more of microwave power density, substrate temperature, deposition rate, and deposition uniformity.

17. The process of claim 15, wherein L1 is held constant and L2 is parametrically varied over a plurality of values to define the plurality of combinations of L1 and L2.

18. The process of claim 15, wherein L2 is held constant and L1 is parametrically varied over a plurality of values to define the plurality of combinations of L1 and L2.

19. The process of claim 15, wherein L1 and L2 are both parametrically varied over a plurality of values to define the plurality of combinations of L1 and L2.

20. The process of claim 15, wherein:

(i) the first microwave chamber, the plasma chamber, and the conductive stage have cylindrical cross sections with radii of R1, R2, and R3, respectively; and

(ii) R3/R2 is about 0.5 or less.

21. A process for depositing a component on a substrate, the process comprising:

(a) providing a microwave plasma assisted reactor comprising;

(i) a plasma chamber comprising an outer wall and defining (A) an upper interior cavity and (B) a lower interior cavity;

(ii) a conductive stage for supporting a substrate holder and having an upper reference surface extending into the plasma chamber lower interior cavity, the conductive stage defining a microwave chamber in the plasma chamber lower interior cavity between the plasma chamber outer wall and the conductive stage; and

(iii) a conducting short adjustably disposed in the microwave chamber below the reference surface by an axial distance L1, the conducting short being in electrical contact with the plasma chamber outer wall and the conductive stage, wherein L1 is capable of adjustment in the reactor by moving the conducting short;

(b) operating the reactor at a selected pressure to deposit a component on the deposition substrate.