Gas-phase precursor seeding for diamond film deposition.

Abstract

A method for depositing an adamantane film that can be used in the fabrication of integrated circuits is described, which method includes treating a substrate on which an adamantane seed layer has been deposited, converting it to a diamond nucleation layer having increased crystallinity compared to the adamantane seed layer, and then growing a complete nanocrystalline diamond film from the diamond nucleation layer.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate to methods of depositing nanocrystalline diamond films, and more particularly, to the deposition of nanocrystalline diamond films during the fabrication of electronic devices, particularly integrated circuits (ICs). [Background technology]

[0002] As the semiconductor industry introduces new generations of integrated circuits (ICs) with higher performance and greater functionality, the density of elements forming those ICs is increasing while the dimensions, size, and spacing between individual components or elements are shrinking. In the past, such reductions were limited only by the ability to define structures using photolithography, but device geometries with dimensions measured in μm or nm have created new limiting factors, such as the conductivity of metal elements, the dielectric constant of insulating materials used between elements, or challenges in 3D-NAND or DRAM processes. These limitations can be addressed by more durable and harder hard masks.

[0003] Conventionally, nanodiamonds (NDs) are seeded onto silicon via ablation or ultrasonic treatment, which creates defects on the wafer surface. Moreover, NDs have high sp 2 From a manufacturing perspective, the ability to dry seed NCD precursors onto silicon allows for the integration of the process into large-scale manufacturing. 3 Adamantane, an extremely volatile molecule with high content, is a potential alternative to ND seeds.

[0004] Diamond, with its excellent hardness, chemical inertness, and high thermal conductivity, has emerged as a promising candidate for a myriad of microelectronic applications. However, the large difference in surface energy between diamond and silicon (approximately 6 J / cm 2, about 1.5J / cm 2 ), the low sticking coefficient of gaseous precursors (e.g., hydrocarbon radicals) and strong competition with non-diamond phases generally result in poor diamond nucleation densities on pristine silicon. Nevertheless, to synthesize high-quality nanocrystalline diamond (NCD) films, >10 11 cm -2 A nucleation density of is targeted.

[0005] To address the issue of nucleation density, substrates are often pretreated (e.g., by mechanical ablation or microchipping) and / or seeded with nanodiamond (ND) particles (~5 nm) prior to deposition. However, the presence of scratches on the substrate surface is detrimental to microelectronic applications. Moreover, the wide particle size distribution and high sp in ND particles can lead to high sp 2 Carbon content is detrimental to the growth of highly smooth, continuous NCD films. Most importantly, these multi-step procedures are cumbersome and not cleanroom compatible. This has motivated a cleanroom-compatible dry seeding procedure capable of depositing a uniform layer of seeds on silicon substrates.

[0006] The smallest "molecular diamond" is adamantane (C 10 H 16 ) possesses a cage-like structure resembling a subunit excised from the diamond crystal lattice. Adamantane and its derivatives, with their extremely small molecular size (<1 nm), have been explored as seeds for the potential growth of diamond in solution and gas-phase seeding systems.

[0007] Nevertheless, adamantane remains difficult to deliver in the gas phase due to its high vapor pressure and low sublimation point. This leads to significant evaporation of adamantane from the substrate, especially at high temperatures and / or in vacuum systems. This subsequently results in low nucleation density and uneven distribution of diamond growth. Therefore, there is a need in the art for an improved method for forming diamond films. Summary of the Invention

[0008] One or more embodiments of the present disclosure are directed to a method of forming a nanocrystalline diamond film, wherein an adamantane seed layer is formed on a substrate by exposing the substrate surface to adamantane vapor in a first plasma process chamber for a first time period, and by forming a nanocrystalline diamond film on the substrate surface by exposing the substrate surface to adamantane vapor in a first plasma process chamber for a first plasma time period. The The adamantane seed layer is formed by generating a plasma of 1. The adamantane seed layer is converted into a diamond nucleation layer having increased crystallinity compared to the adamantane seed layer. A fully nanocrystalline diamond film is grown from the diamond nucleation layer.

[0009] So that the above-recited features of the present disclosure may be understood in detail, a more particular description of the present disclosure briefly summarized above may be made by reference to embodiments, some of which are illustrated in the accompanying drawings. It should be noted, however, that the accompanying drawings illustrate only typical embodiments of the present disclosure and therefore should not be considered limiting of its scope, since the present disclosure may admit of other equally effective embodiments. The embodiments described herein are illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings, in which like reference numerals indicate similar elements. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 illustrates a flow diagram of a method according to one or more embodiments of the present disclosure. [Figure 2A]1A-1C illustrate cross-sectional schematic views of a substrate during a method according to one or more embodiments. [Figure 2B] 1A-1C illustrate cross-sectional schematic views of a substrate during a method according to one or more embodiments. [Figure 2C] 1A-1C illustrate cross-sectional schematic views of a substrate during a method according to one or more embodiments. [Figure 2D] 1A-1C illustrate cross-sectional schematic views of a substrate during a method according to one or more embodiments. [Figure 2E] 1A-1C illustrate cross-sectional schematic views of a substrate during a method according to one or more embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0011] Before describing several example embodiments of the present disclosure, it is to be understood that the present disclosure is not limited to the details of construction or process steps set forth in the following description. The present disclosure is capable of other embodiments and of being practiced or of being carried out in various ways.

[0012] As used herein, "substrate" refers to a substrate or a material surface formed on a substrate on which a film treatment is performed during a manufacturing process. For example, substrate surfaces on which treatment can be performed include materials such as silicon, silicon oxide, strained silicon, silicon-on-insulator (SOI), carbon-doped silicon oxide, amorphous silicon, doped silicon, germanium, gallium arsenide, gallium nitride, glass, sapphire, and any other materials such as metals, metal nitrides, metal alloys, and other conductive materials, depending on the application. Substrates include, but are not limited to, semiconductor wafers. Substrates may be subjected to pretreatment processes to polish, etch, reduce, oxidize, hydroxylate, anneal, and / or bake the substrate surface. In addition to film treatments performed directly on the substrate surface itself, in the present disclosure, any of the disclosed film treatment steps may be performed on an underlayer formed on the substrate, as disclosed in more detail below, and the term "substrate surface" is intended to include such underlayers as the context dictates. As an example, if a film / layer or partial film / layer is deposited onto a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface.

[0013] As used herein and in the appended claims, the terms "precursor," "reactant," "reactive gas," and the like are used interchangeably to refer to any gas species capable of reacting with the substrate surface.

[0014] The phrase "nanocrystalline diamond" as used herein refers to a solid film of diamond typically grown on a substrate, such as silicon. In one or more embodiments, nanocrystalline is the result of enhanced renucleation reactions during diamond growth, where diamond crystal growth is hindered by fluctuations in the surrounding environment, such as the amount of radical species, temperature, and pressure. In one or more embodiments, the nanocrystalline diamond layer is primarily composed of small diamond crystals, either nanospherical or nanocolumnar, and amorphous carbon, typically distributed between the surrounding crystals or accumulated at the grain boundaries. Nanocrystalline diamond is used as a hard mask material for semiconductor applications due to its chemical inertness, optical transparency, and good mechanical properties.

[0015] As used herein, the term "adamantane" refers to a broad class of adamantanes that includes, but is not limited to, commercially available and / or self-synthesized adamantane, its derivatives, oligomers, and polymers.

[0016] Embodiments of the present disclosure describe the development and utilization of a novel method for dry seeding of adamantane onto silicon via vapor-phase delivery. This disclosure demonstrates the seeding, conversion, and growth of adamantane into nanocrystalline diamond films. In this work, adamantane vapor was released into a chamber in a controlled manner and seeded onto a silicon substrate. The seeded sample then underwent incubation and main growth, during which the adamantane "seeds" underwent a series of transformations to form NCD films.

[0017] Due to the high volatility of adamantane, few studies have successfully demonstrated seeding of adamantane vapor-phase delivery, and the resulting films have been essentially non-uniform or diamond-like carbon. Instead, most attempts have involved wet-chemical synthesis or preparation. Even then, NCDs have only been observed in localized islands. One or more embodiments of the present disclosure provide in situ vapor-phase delivery of adamantane and dry seeding of adamantane for the deposition of uniform NCD films.

[0018] Some embodiments of the present disclosure advantageously provide a method that, unlike ultrasonic processing, preserves the integrity of the wafer surface and reduces the probability of defects. Some embodiments provide a dry seeding process that allows for the integration of various processes, which is beneficial for tool development and large-scale production. The small molecular size and high sp 3 The content can potentially help to achieve higher hardness and modulus NCD films while maintaining low surface roughness.

[0019] Conventional multi-step solution-based seeding of NCDs is cumbersome and not cleanroom compatible. Embodiments of the present disclosure provide methods for vapor-phase delivery and dry seeding of adamantane onto silicon substrates for subsequent growth of NCD films. One or more embodiments of the method are in situ and cleanroom compatible.

[0020] Device fabricators using carbon-based hardmask layers require the following requirements to be met: (1) high selectivity of the hardmask during dry etching of the underlying material, (2) low film roughness, (3) low film stress, and (4) film peelability. As used herein, the term "dry etching" generally refers to etching processes in which the material is not decomposed by immersion in a chemical solution, and includes methods such as plasma etching, reactive ion etching, sputter etching, and gas-phase etching.

[0021] In one or more embodiments, a nanocrystalline diamond layer is formed on a substrate. The process of one or more embodiments advantageously results in a nanocrystalline diamond layer with high density, high hardness, high etch selectivity, low stress, and excellent thermal conductivity.

[0022] Hard masks are used as etch stop layers in semiconductor processing. Ashable hard masks have a chemical composition that allows them to be removed by a technique called ashing once they have served their purpose. Ashable hard masks are generally composed of carbon and hydrogen with trace amounts of one or more dopants (e.g., nitrogen, fluorine, boron, silicon). In a typical application, after etching, the hard mask has served its purpose and is removed from the underlying layer. This is generally accomplished, at least in part, by ashing, also known as "plasma ashing" or "dry stripping." The substrate with the hard mask to be ashed, i.e., typically a partially fabricated semiconductor wafer, is placed in a chamber under vacuum, oxygen is introduced, and radio frequency power is applied, creating oxygen radicals (plasma). The radicals react with the hard mask, oxidizing it to water, carbon monoxide, and carbon dioxide. In some cases, for example, when the ashable hardmask leaves behind some residue that cannot be removed by ashing alone, complete removal of the hardmask can be achieved by performing an additional wet or dry etching process after ashing.

[0023] Hard mask layers are often used in narrow and / or deep contact etching applications where the photoresist may not be thick enough to mask the underlying layers, especially as critical dimensions shrink.

[0024] V-NAND or 3D-NAND structures are used in flash memory applications. V-NAND devices are vertically stacked NAND structures with many cells arranged in blocks. As used herein, the term "3D-NAND" refers to a type of electronic (solid-state) non-volatile computer storage memory in which memory cells are stacked in multiple layers. 3D-NAND memory generally includes multiple memory cells that include floating gate transistors. Traditionally, 3D-NAND memory cells include multiple NAND memory structures arranged in three dimensions around a bit line.

[0025] A key step in 3D-NAND technology is slit etching. As the number of tiers increases at each technology node, the thickness of the hard mask film must increase proportionally to withstand the high-aspect ratio etch profile required to control the slit etch profile. Currently, amorphous carbon (aC:H) films are used due to their high hardness and tendency to delaminate after slit etching. However, amorphous carbon hard mask films suffer from delamination at the bevel and poor morphology, leading to pillar striations.

[0026] 1 and 2A-2E, one or more embodiments of the present disclosure are directed to a method 100 of forming a nanocrystalline diamond film. In step 110, a substrate 200 having a substrate surface 205 is exposed to adamantane vapor 210 in a first plasma process chamber 310. The adamantane vapor 210 is applied to the substrate surface 205 for a first time period T1. The substrate surface 205 is then subjected to a first plasma time period T2 to form an adamantane seed layer 220 on the substrate surface 205. P1 In the first plasma process chamber The In some embodiments, the adamantane seed layer 220 is exposed to a plasma 215 in the first plasma process chamber. The1 plasma 215. In some embodiments, the adamantane seed layer 220 is formed by a thermal process (meaning without plasma exposure).

[0027] The first plasma process chamber 310 can be any suitable plasma chamber with any suitable plasma source (e.g., remote, microwave, capacitively coupled plasma (CCP), or inductively coupled plasma (ICP)), such as one of the process chambers described above. In some embodiments, the flow rates and other process parameters described below are for a 300 mm substrate. It should be understood that these parameters can be adjusted based on the size of the substrate being processed and the type of chamber used without deviating from the embodiments disclosed herein. In certain embodiments, , th The plasma 215 comprises one or more of a capacitively coupled plasma, an inductively coupled plasma, a pulsed discharge plasma, a hot filament, or an electron cyclotron resonance plasma.

[0028] In some embodiments, the first plasma 215 is a gas containing argon (Ar), molecular nitrogen (N), empirical formula C x H y , where y is 2x+2, 2x, or 2x-2, carbon dioxide (CO), or molecular hydrogen gas (H). In some embodiments, adamantane vapor is co-flowed with the first plasma gas. In some embodiments, adamantane vapor is not flowed during plasma generation.

[0029] In some embodiments, the first plasma 215 is generated using a power greater than 50 Watts, 100 Watts, or 150 Watts. In some embodiments, the substrate 200 is maintained at a temperature in the range of 20-600° C. during the formation of the adamantane seed layer 220.

[0030] In some embodiments, forming the adamantane seed layer 220 comprises two or more cycles of exposure to the adamantane vapor 210 and the first plasma 215. In some embodiments, forming the adamantane seed layer 220 comprises in the range of 1 to 1000 cycles of exposure to the adamantane vapor and the first plasma.

[0031] The first plasma processing chamber 310 of some embodiments includes a showerhead / electrode 312 (also referred to as a first plasma source) located a first distance D1 from the substrate surface 205. In some embodiments, the first distance D1 is greater than or equal to 10 mm, 15 mm, 20 mm, or 25 mm.

[0032] In step 120, the adamantane seed layer 220 is converted to a diamond nucleation layer 230. The diamond nucleation layer 230 is the adamantane seed layer 220 after a partial crystallization process. The conversion to the diamond nucleation layer 230 is a partial conversion process in which at least a portion of the crystalline properties of the adamantane seed layer 220 are increased.

[0033] The adamantane seed layer 220 of some embodiments is a second plasma generated by a plasma source 325. Nopu The diamond nuclei are converted to a diamond nuclei layer 230 in a second plasma process chamber 320 using a plasma 225. The second plasma process chamber can be any suitable plasma chamber with any suitable plasma source (e.g., remote, microwave, capacitively coupled plasma (CCP), or inductively coupled plasma (ICP)), such as one of the process chambers described above. In some embodiments, the flow rates and other process parameters described below are for a 300 mm substrate. It should be understood that these parameters can be adjusted based on the size of the substrate being processed and the type of chamber used without deviating from the embodiments disclosed herein. In certain embodiments, , thThe second plasma 225 comprises one or more of a capacitively coupled plasma, an inductively coupled plasma, a pulsed discharge plasma, a hot filament, or an electron cyclotron resonance plasma.

[0034] In some embodiments, the second Nopu Plasma 225 is a gas that contains argon (Ar), molecular nitrogen (N2), and empirical formula C x H y , where y is 2x+2, 2x, or 2x-2, carbon dioxide (CO), or molecular hydrogen gas (H). In some embodiments, adamantane vapor is co-flowed with the first plasma gas. In some embodiments, adamantane vapor is not flowed during plasma generation.

[0035] In some embodiments, the second plasma 225 is generated using a second plasma source with a power less than or equal to 10 kilowatts, 9 kW, 8 kW, 7 kW, 6 kW, 5 kW, or 4 kW. In some embodiments, the second plasma 225 is a pulsed plasma with a duty cycle less than or equal to 75%, 70%, 65%, 60%, 55%, 50%, 45%, or 40% at a frequency in the range of 50 Hz to 100 Hz, or in the range of 60 Hz to 90 Hz, or in the range of 70 Hz to 80 Hz. In some embodiments, the second plasma 225 is operated in a continuous mode (100% duty cycle). In some embodiments, the second plasma 225 is pulsed with a duty cycle less than or equal to 75%, 70%, 65%, 60%, 55%, 50%, 45%, or 40% at a frequency in the range of 50 Hz to 100 Hz, or in the range of 60 Hz to 90 Hz, or in the range of 70 Hz to 80 Hz. In some embodiments, the second plasma 225 is operated in a continuous mode (100% duty cycle). Nopu The plasma 225 has a power less than or equal to 6 kW with a duty cycle less than or equal to 50% at a frequency in the range of 70 Hz to 80 Hz. In some embodiments, the substrate 200 is maintained at a temperature in the range of 50-600° C. during conversion of the adamantane seed layer 220 to the diamond nucleation layer 230.

[0036] In some embodiments, the substrate 200 is located at a second distance D2 from the plasma source 325. In some embodiments, the substrate 200 is located at a distance D2 less than or equal to 12 cm, 11 cm, 10 cm, 9 cm, or 8 cm from the plasma source 325. In some embodiments, the second plasma source 325 comprises a showerhead that acts as an electrode. 。

[0037] The diamond nucleus layer 230 has an increased crystallinity compared to the adamantane seed layer 220. In some embodiments, the crystallinity of the diamond nucleus layer 230 is increased by greater than or equal to 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%.

[0038] In step 130, an intact nanocrystalline diamond film 240 is grown from the diamond nucleation layer 230. The term "grown" as used in this manner means that the intact nanocrystalline diamond film 240 is formed on the diamond nucleation layer 230 and may incorporate the diamond nucleation layer 230 into the intact nanocrystalline diamond film 240. The intact nanocrystalline diamond film 240 may be epitaxially grown or deposited by any suitable technique known to those skilled in the art.

[0039] In some embodiments, growing the complete nanocrystalline diamond film 240 is performed in the second plasma process chamber 320 using a third plasma 235 (sometimes referred to as a strong plasma). In some embodiments, the complete nanocrystalline diamond film 240 is , guideThe nanocrystalline diamond film 240 is grown using an electrochemical / inductively coupled plasma, a microwave plasma, a pulsed discharge plasma, a hot filament, or an electron cyclotron resonance plasma. In some embodiments, the complete nanocrystalline diamond film 240 is grown using an intense microwave plasma. In some embodiments, the complete nanocrystalline diamond film 240 is formed in a different process chamber using a second plasma 225. In some embodiments, the complete nanocrystalline diamond film 240 is formed in the same process chamber as the adamantane seed layer 220 and / or the diamond nucleus layer 230.

[0040] In some embodiments, the third plasma 235 comprises a microwave plasma having a power greater than or equal to 50 W, 3 kW, 4 kW, or 5 kW with a duty cycle greater than or equal to 60%, 65%, 70%, 75%, or 80%.

[0041] In some embodiments, the substrate 200 is maintained at a temperature in the range of room temperature (25° C.) to 750° C. during exposure to the third microwave plasma. Third The temperature is maintained at room temperature (25°C), 50°C, 75°C, 100°C, 150°C, 200°C or above 250°C during exposure to the microwave plasma 235.

[0042] During step 130, substrate 200 is positioned a distance D3 from plasma source 325. In some embodiments, distance D3 is the same as distance D2. In some embodiments, distance D3 is reduced from distance D2. In some embodiments, substrate 200 is positioned less than 12 cm, 11 cm, 10 cm, 9 cm, or 8 cm. Third Located at a distance from the microwave plasma source.

[0043] In some embodiments, to prepare the supply of adamantane vapor, 1-100 g of adamantane can be transferred into an ampoule connected to the chamber and preheated to between 25-100° C. In some embodiments, a single silicon wafer is loaded into the capacitively coupled plasma (CCP) chamber. , pu In some embodiments, the cleaning may be carried out by plasma. , pu After the plasma, the adamantane gas mixture may be supplied for a period of time. 、C x H 2x+2 The / CO2 / H2CCP is struck at between 50 and 800 W for 1 to 3600 seconds to facilitate the adsorption of adamantane onto the silicon substrate. This seeding procedure can be repeated for 1 to 1000 cycles. In some embodiments, the stage temperature is maintained below 600°C throughout the process, and the gap between the stage and the plasma source can be set to greater than or equal to 10 mm.

[0044] In some embodiments, the seeded wafer is then transferred to a microwave (MW) plasma CVD chamber for the subsequent incubation and main growth process. C with a power greater than 50 W and a duty cycle of 10-100%. x H 2x+2 A CO2 / H2 MW plasma is generated, the substrate support temperature is maintained between 50°C and 600°C, and the gap between the substrate and the plasma source is maintained at less than 12 cm.

[0045] In some embodiments, after 0.5 to 6 hours of incubation, a third microwave plasma is applied at 50 W to 12 kW and a duty cycle of 60 to 100% for forming an intact nanocrystalline diamond film, step 130. The substrate support is maintained at a temperature of 100 to 750°C and a gap of less than 10 cm, respectively, for more than 2 hours.

[0046] In some embodiments, the substrate is then ThirdAfter an additional 2-10 hours of primary growth using microwave plasma, the small diamond particles continue to grow and eventually form a well-faceted, nearly fully coalesced NCD film, in some embodiments.

[0047] References throughout this specification to "one embodiment," "some embodiments," "one or more embodiments," or "an embodiment" mean that a particular feature, structure, material, or characteristic described in connection with an embodiment is included in at least one embodiment of the present disclosure. Thus, the appearances of phrases such as "in one or more embodiments," "in some embodiments," "in one embodiment," or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment of the present disclosure. Moreover, particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0048] Although the disclosure herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed method and apparatus without departing from the spirit and scope of the disclosure. It is hereby intended that the disclosure cover modifications and variations that come within the scope of the appended claims and their equivalents.

Claims

1. 1. A method of forming a nanocrystalline diamond film, comprising: forming an adamantane seed layer by exposing a substrate surface to adamantane vapor in a first plasma processing chamber for a first time period and generating a first plasma in the first plasma processing chamber for a first plasma time period; converting the adamantane seed layer into a diamond nucleus layer having increased crystallinity compared to the adamantane seed layer; growing an intact nanocrystalline diamond film from said diamond nucleation layer; A method comprising:

2. 10. The method of claim 1, wherein forming the adamantane seed layer comprises in the range of 1 to 1000 cycles of exposure to the adamantane vapor and the first plasma.

3. 10. The method of claim 1, wherein the first plasma processing chamber comprises a showerhead / electrode located at a first distance from the substrate surface, the first distance being greater than 10 mm.

4. The method of claim 1 , wherein the first plasma comprises one of a conductive / inductively coupled plasma, a microwave plasma, a pulsed discharge plasma, or an electron cyclotron resonance plasma.

5. The first plasma is a mixture of argon, nitrogen, empirical formula C ｘ H ｙ 5. The method of claim 4, wherein the reactant comprises one or more of an organic species having a y of 2x+2, 2x, or 2x-2, carbon dioxide, or molecular hydrogen gas.

6. The method of claim 4 , wherein the first plasma has a power greater than 50 watts.

7. The method of claim 4, wherein the substrate is maintained at a temperature between 20 and 600°C.

8. 10. The method of claim 1, wherein converting the adamantane seed layer into the diamond nucleation layer occurs in a second plasma process chamber using a second plasma comprising a second plasma source.

9. The method of claim 8 , wherein the second plasma comprises any of a conductive / inductively coupled plasma, a microwave plasma, a pulsed discharge plasma, or an electron cyclotron resonance plasma.

10. The method of claim 9 , wherein the second plasma comprises one or more of the following: a power of less than 10 kW.

11. The method of claim 9 , wherein the substrate is positioned at a distance from the second plasma source of less than 10 cm.

12. The method of claim 9, wherein the substrate is maintained at a temperature in the range of 50°C to 600°C.

13. 10. The method of claim 1, wherein growing the nanocrystalline diamond film is carried out in a second plasma process chamber using a third plasma selected from conductive / inductively coupled plasma, microwave plasma, pulsed discharge plasma, or electron cyclotron resonance plasma.

14. 14. The method of claim 13, wherein the third plasma comprises one or more of: a power greater than 50 W with a duty cycle greater than 60%.

15. The method of claim 13, wherein the substrate is maintained at a temperature in the range of room temperature to 750°C.

16. The method of claim 13 , wherein the substrate is positioned at a distance from the second plasma source of less than 10 cm.

17. 1. A method of forming a nanocrystalline diamond film, comprising: forming an adamantane seed layer by exposing a substrate surface to adamantane vapor in a first plasma processing chamber for a first time period and generating a first plasma in the first plasma processing chamber for a first plasma time period, the first plasma comprising a mixture of argon, nitrogen, and a fluorine-containing compound of empirical formula C; ｘ H ｙ forming an adamantane seed layer comprising one or more of an organic species having a molar ratio of 1:1, where y is 2x+2, 2x, or 2x−2, carbon dioxide, or molecular hydrogen gas, wherein the substrate surface is located at a first distance from a first plasma source in the first plasma processing chamber that is greater than or equal to 10 mm; converting the adamantane seed layer into a diamond nuclei layer having increased crystallinity compared to the adamantane seed layer in a second plasma process chamber using a mild second plasma, wherein a second plasma source generates the second plasma having one or more of a power of less than 10 kW and the substrate surface is located at a distance of less than 10 cm from the second plasma source; growing an intact nanocrystalline diamond film from the diamond nuclei layer in the second plasma process chamber using a third plasma having one or more of a power greater than 50 W with a duty cycle greater than 60%; A method comprising:

18. 18. The method of claim 17, wherein forming the adamantane seed layer comprises in the range of 1 to 1000 cycles of exposure to the adamantane vapor and the first plasma, the first plasma comprising either a conductive / inductively coupled plasma, a microwave plasma, a pulsed discharge plasma, or an electron cyclotron resonance plasma, having a power greater than 50 watts, and the substrate is maintained at a temperature between 20 and 600°C.

19. 20. The method of claim 18, wherein the second plasma comprises one of a conductive / inductively coupled plasma, a microwave plasma, a pulsed discharge plasma, or an electron cyclotron resonance plasma, and the substrate is maintained at a temperature in the range of 50°C to 600°C.

20. 20. The method of claim 19, wherein growing the integral nanocrystalline diamond film is carried out by maintaining the substrate at a temperature in the range of room temperature to 750°C, and the substrate is located at a distance from the plasma source of less than 10 cm.

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