TW200416197A - Boron doped diamond - Google Patents

Abstract

A layer of single crystal boron doped diamond produced by CVD and having a total boron concentration which is uniform. The layer is formed from a single growth sector, or has a thickness exceeding 100 μm, or has a volume exceeding 1 mm<SP>3</SP>, or a combination of such characteristics.

Description

说明 Description of the invention (The description of the invention should be stated: the technical field, prior art, content, embodiments, and drawings of the invention are briefly described.) [Technical field to which the invention belongs] Background of the invention The present invention relates to doped diamonds, More specifically, it is about diamonds manufactured by Chemical Vapour Deposition (hereinafter referred to as CVD diamonds). For a diamond that can be widely used, the special size, uniform doping concentration, and electronic and / or optical-related properties of the doped diamond layer body are all advantageous. Depending on the content of their application, this material needs to substantially eliminate harmful traps or defects with electronic or optical activity. No such material is currently available. For applications such as high-power electronics, a large 15-type film independent diamond with a thickness of 50-100 mm and a side area in the range of i x lmm2-50 x 50mm2 is required. For a viable production in a competitive market, diamonds for use in these structures are advantageously grown from a large material and processed into the final product. In addition, large pieces can be processed for wafer dicing, and the cost of finished product manufacturing can be reduced. For optical applications such as filter membranes and energy-absorptive measuring devices, the raw material for large-size materials is a 20% requirement on the nature of the device. Therefore, synthesizing thick layer bodies has multiple benefits. Boron is the only diamond inclusion known to have good, rather shallow, doped performance characteristics. It is reported in the literature that other potential superficial inclusions that are still in development include: sulfur, phosphorus (O &gt;), oxygen (〇), warp (u), but these are not yet a large number of reliable (k) impurities Thing. There are many electric applications that need to disturb diamonds. 6 200416197 发明, invention description, sub-applications, etc. are usually on a large area and need to have uniform characteristics. However, doped boron in synthesis is a very sensitive property of this particular cell. Polycrystalline diamonds contain a kind of randomly selected crystal growth tank. However, although the average concentration of boron is uniform on a scale larger than the particle size, it is on the same scale as the particle wealth. The local butterfly concentration is at the point and point. There are substantial differences between them. Inclusions can also be incorporated by post-growth processing. At present, the only reliable crystal post-treatment suitable for diamond is ion implantation, and it is a method that can be used to make laminated diamond structures without heterogeneity 10. For example, a 'ρ_Γ (ρ_-type essence) structure can be manufactured by using a dose and energy suitable for implanting boron into a high-quality natural Ila-type diamond. Unfortunately, residual damage (voids and cracks) often occurs under ion implantation. Although annealing can reduce such damage, such damage cannot be completely removed. The damage will result in the degradation of the charged carrier due to the scattering of boron receptors and poor compensation. Methods for depositing or growing, for example, diamond, on a substrate by chemical vapor deposition (CVD) are currently established and widely described in patents and other literature. Since diamond is deposited on a substrate by CVD, these methods usually involve providing a gaseous mixture that, when dissociated, can provide hydrogen in the form of a king atom or a halogen (eg, fluorine, gas), and Carbon or carbon-containing free radicals and other reactive substances (for example: CHx, CFX, where X can be 疋 1 to 4). In addition, oxygen-containing sources can be present as well as sources that provide nitrogen and boron. An inert gas such as helium, neon or argon may also be present in a variety of methods. Therefore, a typical source gas (sourCe gas) mixture 7 200416197 玖, description of the invention. Will contain: hydrocarbons (CxHy, where X and y can each be 1 to ι〇) or toothed carbon (CxHyHalz, where X and z may each be 1 to 10, and y may be 0 to 10) and one or more of the following: COx (where X may be 0 to 2), 〇2, H2, N2, NH3, B2H6 and an inert gas. Each gas can exist in its natural isotope ratio, or it can be artificially controlled relative isotope ratio; for example, hydrogen can exist in deuterium or tritium, and carbon can exist in 13C. The source gas mixture can be dissociated by an energy source, such as microwave, RF (high frequency) energy, a flame, a hot tungsten wire, or a jet-based technology, and allow such borrowing This produces 10 reactive gases that are deposited on a substrate to form a diamond. CVD diamond can be produced on a variety of different substrates. Depending on the nature of the substrate and the chemical nature of the manufacturing method, polycrystalline or single crystal CVD diamonds can be made. For many other dopants, it is less difficult to get boron dopants into the solid during the deposition process. The doping ratio of boron in the solid is the concentration of boron (B) versus carbon (C) doped with 15 ([B] / [C]: solids) compared to [B] / [C]: gases of the deposition gas. In other words, usually (within the {100%} crystal growth tank) is about work, and it can be different depending on various factors. There are various methods by which CVD diamond can be doped with boron in the manufacturing process. With microwave money, hot wire and arc spray technology, diborane (B ^ 6) or some other suitable gas can be added to the gas stream, 4 ^ into the gas can be pumped into methanol or propane containing the oxidation side The rotten acid powder can be placed in the crystal trough or inserted into the electrode in the plasma. In terms of crystal growth by the L: k flame method, a methanol mist containing boric acid can be injected into the gas stream with a sprayer. Diamond films can also be doped under unintentional circumstances. For example, Dianzhan has decomposed a substrate made of boric acid 8 200416197, description of the invention. Nitrogen can also be introduced into the synthesized plasma in various forms. Typical examples are nitrogen (N2), ammonia (nh3), air, and diborene (b2h4). Although high-quality single crystal (SCV) CVD diamonds play an important role in high-energy electronics, the number of potential applications must only be achieved if a CVD doped diamond with uniform and excellent electronic properties is available Substantial increase. In addition, boron doped diamonds can also be used in other applications where boron (B) doping can advantageously produce uniform color, brightness, or other related properties. 10 [Akiuchi 3 Summary of the Invention According to the first aspect of the present invention, the present invention provides a boron doped diamond made by vapor deposition (CVD), wherein the overall concentration of boron dopant is uniform 'in most of the volume. The difference is less than 50%, and preferably less than 15 2%. It is less than 50μm measured by a lateral analysis at each measurement point. It is better to use a lateral analysis at each measurement point. It is measured to be less than 30 μm and has at least one of the following characteristics: The sacral layer system is formed from a single, preferably a single crystal growth tank composed of {1〇〇}, {113}, {111}, and {110}, And even better are these 20 {100} crystal troughs. The thickness of the (H) layer body is more than 100 μm, and more preferably 500 μm, and the volume of the (lii) layer body is more than 1 mm3, more preferably more than 10 mm3, and even more preferably more than 30 mm3. The term "most layers, 'used in this specification and applied for patent 9 200416197', the description of the invention means at least 70% of the total volume of the diamond layer, preferably more than 80% 'and more preferably It is greater than 95%. The CVD single crystal boron doped diamond layer of the present invention may also contain nitrogen as a kind of dopant. The diamond layer generally contains a nitrogen concentration of no more than ι / 5 boron concentration of 5 degrees, and It is preferably lower than the concentration of boron 丨 / 50. The diamond layer body preferably has "excellent crystalline properties." This "excellent crystalline property allows boron atoms and nitrogen atoms to exist as impurities and point defects such as inclusions, voids, hydrogen, and the like. It can also be used in this way. Most of the volume of the diamond has one or more of the following characteristics, the majority of the volume is as defined above. (A) The layer contains a type that is higher than 1 X 1〇i4 atoms / em3 and lower than 1 X. An uncompensated boron concentration of 10 μatoms / cm3, preferably an uncompensated boron concentration higher than 1 X 10 atoms / cm3 and lower than 2 x 1019 atoms / cm3, and more preferably a higher than 5 χ 1〇i5 atoms / cm3 and less than 2 X 1〇〗 8 atoms 15 / cn &gt; 3 uncompensated boron concentration, (b) — a hole mobility measured at 300K ((ih) is greater than χ 2.1 χ 1010 / (Nh0 · 52) When Nh is less than or equal to 8 χ 1015 atoms / cm3 (function 1) 20 χ 1 χ 1018 / Nh When Nh is greater than 8 χ 1015 atoms / cm3 (function 2) where Nh Is the hole concentration (or equivalent, the concentration of the ionized boron acceptor) '~ The function relationship with Nh is based on the current model and the value of g represents the maximum 10 kan, which is a good description of the invention The existing reading. G is a value greater than M, and preferably a value greater than 1.4, and more preferably a value greater than 17, even more preferably greater than 2.0. (C) Has a nitrogen-gap ( N_V) Chrominaceous correlation at 575nni &amp; 637nm is weak or no cold light characteristics. In particular, when measured at 77K with 纟 丨 such as argon ion laser excitation, the nitrogen void is at 575nm compared with the peak of ㈠ ~ ㈤ The integrated intensity of the zero phonon spectral line is less than 1/50 of the integrated intensity of the Raman line of the diamond falling at 1332 cm · 1, preferably less than 1/100 'and more preferably less than 1/300. (D) —The FWHM of the Raman spectrum measured at 300K with 514 nm argon ion laser excitation is less than 4 cm · 1, preferably less than 3 cm-1, and more preferably Is less than 2 5cm_]. (E) When measured with a Fourier Transform Infrared Spectrometer (FTIR) using the following method, its uncompensated boron concentration has a high degree of heterogeneity. In particular, the distribution frequency of the uncompensated boron concentration A representative sample taken from this layer was obtained using a Fourier transform infrared spectrometer (FTIR). For measurement, the difference in 90% of the measurement, expressed as a percentage of the average value, is less than 50%, and more preferably less than 300 / 〇. Σ) Under ultraviolet excitation, use the following method 238 nmi bound exciton scattering (ΒΕ) was measured at 77K. The combined exciton scattering (ΒΕ) was consistent with the solid indifference of the uncompensated substitution of butterfly atoms. In particular, the BEE frequency distribution measured by this method has a difference of 90% of its measurement on any surface of the layer or the sample of the layer, and the average value is the average value. The percentage indicates that it is less than the article, and more preferably less than 30%. 200416197 发明, description of the invention (g) Under the excitation of ultraviolet rays, the free exciton scattering intensity measured at 77κ using the following method is highly homogeneous. In particular, the frequency distribution of FE measured by this method, under any one of the representative surfaces or samples of the layer, the difference of 9 ()% of the amount, with the average value The percentage indicates that it is less than ⑽, more preferably less than 30%. It is surprising to find that the high mobility in the CVD diamond of the present invention is high. The current mobility difference pattern for carriers (or ionized acceptors) with a concentration of more than 8 x 10 ls atoms / cm3 for these carriers is based on the assumption that boron atoms with 10 acceptors are the main scattering mechanism 'and The nature of its distribution is based on its existence. So this pattern implies that it is impossible to reach a value higher than this. Conversely, the results of the present invention described in this beta book indicate that this mode is wrong, because the mobility of the doped diamonds reported in the previous literature is limited to other ones that can be removed Factor.丨 5 The CVD single crystal boron doped diamond layer of the present invention may be a layer or an area where the surface film is independent or constitutes a larger diamond body or layer. The larger diamond layer or body may be a single crystal or polycrystalline diamond manufactured by CVD or other synthetic methods. The larger diamond layer or body can be doped with boron, nitrogen, or other elements. : 0 The diamond layer body or individual of the present invention may be in the form of a gem. According to another aspect of the present invention, the present invention provides a kind of doped single crystal CVD diamond layer body. This method includes the steps of: providing a diamond substrate with a surface substantially free of crystal defects, providing a source gas (this source gas contains a boron 12 200416197 玖, the source of the invention description), and decomposing the The source gas then allows the homogeneous epitaxial diamond to grow on the surface that is substantially free of crystal defects, thereby producing a single crystal boron doped diamond layer, preferably having the above type. The basic requirement of this method is that the diamond must be grown on a surface that is substantially free of crystal defects 5. The method of the present invention may additionally include the use of a controlled addition of nitrogen to the source gas. The nitrogen in the source gas can provide additional control over the shape produced by the growing single crystal, and the doping ratio of nitrogen will be substantially lower than that of boron. Therefore, the addition of nitrogen, calculated in terms of nitrogen molecules, is within the range of higher than 100.5 and lower than looooppm, and more preferably within the range of higher than 1,000ppm, and more preferably within the range In the range of higher than 3 and lower than 200 Ppm, because the boron of the doped material exists as a scattering color core, it does not have a significant negative impact on the electronic characteristics of the boron doped layer, and it will significantly increase {100} The size of the crystal growth groove, and the size of 15 competitive crystal growth grooves (for example: {Hi}) is reduced. This means that, for growing on a {100} plate, the added nitrogen can cause it to grow while maintaining a substantial {100} crystal growth tank. Those skilled in the art can understand that the stage of using nitrogen to change the shape can be separated from it or continue the stage of the uniform boron doped layer growth. 20 Therefore, the uniform boron doped diamond of the present invention can be applied to a wide range of fields, such as: electrons, tritium testers, high-energy electrons, and the like. In addition, boron doped diamonds can also be used in other applications where boron (B) doping can advantageously produce uniform color, brightness, or other related characteristics. For example, in some applications such as a cutting knife, boron can be used to make the diamond 13 200416197. Description of the invention Stone has a color, thereby improving visual control, and the uniformity of its color can be used as a factor indicating quality. Optionally, the iron stone can be used for decorative applications of polished gemstones. Generally, the uniformity of color can be used as a factor indicating quality. 5 For the various applications mentioned above, the body or layer of the diamond can be produced, for example, by cutting two or more and usually a large number of small particles or units for use in one or more of the above In use. The size of the particles or cells depends on their application. C lean application mode: | 10 Detailed description of the preferred embodiment In addition to the above features, the single crystal boron doped Cvd diamond layer body of the present invention may have one or more of the following features in most of its volume, and most of the features The system is as defined above: 1 Scattered by any single impurity: silicon (si), phosphorus, thionium, nickel 15 (Ni), cobalt (Co), aluminum (A1), manganese (Μη), and iron free exciton scattering (FE) constitutes a level of not more than 1 ppm * and a total amount of these impurities is not more than 5 ppm. The above-mentioned "impurities" do not contain hydrogen and its isotopes. 2 · A cathode cold light (CL) emission signal falling in the wide band of 57511111 is very low 20 or absent, and one is excited by a 514nm argon ion laser at 77K (called The optical cold light (PL) correlation spectral line measured with a 300 mW incident beam) has a peak integrated area that is smaller than or 1/100 times smaller than the integrated area of the peak of 1332 cm-1 &lt; Raman line. It is preferably less than 丨 / 50, and more preferably less than 1/300.

14 200416197 发明, description of the invention 3. In the electron magnetic resonance spectroscopy (EPR), a single charged nitrocellulose [N-C]. The concentration is below 40 ppb, and more typically below IOppb. 4. In the electronic magnetic resonance spectroscopy (EPR), a rotational density at g = 2.0028 is less than 1 X 1017 cm · 3, and more typically less than 5 X 1016 cm · 3. In single 5 crystal diamonds, the line that falls at g == 2.0028 is related to the concentration of lattice defects. Its larger values are typically found in natural Ila diamonds, in CVD diamonds (through depression Plastically breakable), and in poor quality homoepitaxial diamonds. 5. With excellent optical properties, its ultraviolet (UV) / visible light and red 10 outer line (IR) penetration approximates the theoretical maximum value of lib diamonds, and more particularly 'single substitution of nitrogen at 270nm of ultraviolet (UV) The absorption value is very low or absent, and the C-Η absorption bandwidth in the range of 2500 to 3100 cm-1 of the infrared spectrum is small or absent. The characteristic of the absorption spectrum of semiconductor boron doped diamond is a continuous absorption peak starting from the near-infrared spectral region and extending from about 370 meV to about 2.2 eV 15. This absorption peak is responsible for generating blue (light blue for a concentration of ~ 5 x 1015 cm_3, and dark blue to black for a concentration of ~ 5 x 1019 cm-3). Three significant broadbands at 304, 348, and 363 meV can be observed below the continuous broadband threshold of energy, and if observed at high resolution and low temperature, a significant number of structures will be exhibited. 20 6. X-ray topography shows that, in the characteristics related to the crystal, the &lt; 100 &gt; edge line of the original substrate grows outward to form &lt; 11〇 &gt; edge line. Since the potential of compensated nitrogen is substantially lower than that of boron, the uniformity of the distribution in uncompensated sources usually represents the uniformity of all boron concentrations. In addition, the electronic characteristics mainly depend on the uncompensated boron concentration instead of all boron concentrations. 15 200416197 玖, description of the invention 疋 Therefore, the uniformity of the concentration is an important parameter. Diamonds containing uncompensated boron show a single phonon absorption characteristic with a maximum value falling at 1282 (: 11 ^ 1 (159meV). It was found that the uncompensated boron and the broadband absorption coefficient effect on nsacm · 1 The relationship between them is a line of 5 I *. ^ At the temperature measurement, the side concentration in ppm is 1.2 X (the absorption coefficient of 1282cm · 1). The uncompensated rotten diamond also shows An absorption feature falling at 2457cm · 1 that can be revealed by subtracting the essential two-phonon absorption spectrum. When its 1282cm-1 feature is too weak to be used, its uncompensated boron concentration can be 10 using the relationship: The concentration of the unrefined detective stone pentamidine (PPm) = 〇〇〇142 X 2457 ga_1 (11 ^ 乂 111-1) is used to calculate the integral absorbance coefficient which falls at 2457 € 111 · !. In a diamond sample with two sides parallel to each other, a macroscopic measurement of the uniformity of the uncompensated boron concentration can be performed using a Fourier transform infrared 15 spectrometer (FTIR) absorber in the following manner. Representative infrared light spectrum characteristics of a whole sample This can be obtained by collecting a resolution of 0.5 c claw_i at room temperature. And a Fourier Transform Infrared Spectrometer with a 0.5mm angle of view measurement is made. The map contains a minimum of 20 data points. Then, based on its average measurement, select the above relationship-, and Use its 20 to calculate the uncompensated butterfly concentration at each location. Then determine its uniformity from the frequency diagram of its concentration measurement, and evaluate the measurement by its average value far from the limit of the group standard deviation. Ultraviolet cold light spectrum of high-quality rotten diamonds (recorded at 77K) shows that there is very strong combined excitation scattering at 5.22eV (237.5nm), and 16 200416197, and the invention description is at 5.27eV (235.2nm). Free-excitation scattering. For high-quality diamonds with boron concentrations exceeding approximately 1 ppm, the integrated intensity of the two scattering at 77K is approximately proportional to the concentration on the uncompensated side. The relationship is: [uncompensated in ppm Boron concentration] = 1.86 X 1 (combined with excitation intensity 5 1 (free excitation intensity). This ratio at different positions in the entire sample can be used to judge the drill within the approximate range of the measured butterfly concentration. The uniformity of the diamond near the surface area. The sample is coated with a thin layer (5nm) and a uniform layer of gold to avoid charge effects. It is arranged at a temperature of 77K and a scanning electron microscope 10 'and a MonoCL is used. The system was collected with an acceleration voltage of 15kV, a current of 10.2 milliamps, and a point with a size smaller than 10 μιη X 10 μιη. The UV CL characteristics of the sample can be collected by collecting these samples at two intervals of 500 μηι or 1 The line points defined by the intersection of the grid lines intersected by the vertical lines of mm (depending on the approximate area) are plotted, and a minimum of 30:15 data is collected. Then judge from the frequency diagram made by the measured concentration, evaluate the entire width distribution of 90% of the measurement, and express it as a percentage of the average. This method was applied to measure the intensity of combined excitation and free excitation scattering and calculate the ratio of the two intensities. Because there is a significant difference in trapping artifacts that suppress the combined excitation scattering, 20 this is equal to the subsequent increase in the observed combined excitation scattering, unless the combined excitation scattering is completely suppressed everywhere. The existence of a strong free excitation means that it is substantially free of defects such as dislocation and impurities. For individual crystals in polycrystalline CVD diamond synthesis, the correlation between low defect and impurity densities and high free-excitation free-excitation 17 200416197 发明, description of the invention has been previously reported. At higher butterfly levels (typically higher than 20-25 ppm in solids), its free excitation scattering will eventually be suppressed by high boron point defect densities, rather than due to crystal defects such as differential emissions. The uniformity of free excitation scattering is an excellent non-existent 5 local high defect density measurement. A typical secondary ion mass spectrometer (SIMS) analysis method applies a main 02+ electron beam with a main voltage of 10 kV, an electron beam current of typically 1 μA, and a spatial resolution of less than 50 μM. It typically follows the analysis points calibrated at 0.5 mm or imm on the surface of the layer, typically at least 20 points are obtained from each side of 10, and more preferably at least 40 points. Calibration is performed by comparing the implanted standard points. The data obtained from the secondary ion mass spectrometer (SIMS) is analyzed by obtaining the group average, and then the range of the data is used to represent the different percentages of the data group. The two opposite major surfaces of a layer are set to approximately equal weighting points, and a volume of 15 is defined. Below a detection limit of about 2_5 χ 10 &quot; atoms / cm3, the reproducibility of a typical secondary ion mass spectrometer (SIMS) may be in the range of 3_5%. To define the volume of a material, the two opposite surfaces are defined by SIMS and BE / FE spectra, and the thickness of the penetrating sample is defined by infrared (IR) absorption. The resolution of measurement techniques (for SEM analysis for BE, FE and uncompensated boron concentration, and SIMS analysis for all boron concentration) is related to the different types of boron concentration that can be observed in diamonds . For example, in a polycrystalline diamond with a typical particle size of 100 μm, scanning a sample with a 1 mm point of analysis may fall evenly between the individual 18 200416197 玖, invention description grains or crystal growth tanks No substantial difference in boron (B) concentration was observed. When sampling 20 or more data points at a resolution of 50 μm or less, it may be shown that such minor level differences do not exist. For the production of the uniform boron-doped CVD diamond single crystal layer of the present invention, it is important that 5 crystals grow on the surface of a diamond that does not substantially have crystal defects. In this test, the term “defective fatigue” mainly means poor discharge. (Disiocation) and fine W slits also include twin boundaries, point defects that are essentially independent of doped nitrogen, low-frequency scattering boundaries, and any other type of lattice elongation damage. Preferably, the substrate is a low birefringence type electrically neutral 0, lb, or Ila pressure / South temperature synthetic diamond or a cvD synthetic single crystal diamond. Defects can damage materials in two ways: negatively affecting electronic properties (eg, hole mobility) and affecting local boron introduction. Since dislocation multiplication occurs during thick body growth, it is particularly important to control dislocations in the substrate and in the early stages of growth. 5 Defect density The easiest to use a plasma or chemical etch (known as a display plasma etch) that is best suited to visualize the defect for optical inspection. It can be used, for example, as a simple plasma etch of the following type. There are two types of defects: 1) the essence of the quality of the 4 substrate materials. In selected natural diamonds, these flaw densities can be as low as 50 / mm2, more typically 10/1111112, or sometimes as high as 106 / mm2 or higher. 2) Those produced by polishing include fine cracks formed by the differential structure along the polishing line and micro-cracks. These densities may differ in a sample 'in poorly polished areas or samples. Typical values are 19 200416197 发明, invention description is in the range of about 102 / mm2 to more than 104 / mm2. In terms of the surface etching characteristic density related to defects as described above, the defect density is preferably less than 5 X 10 / mm2, and more preferably less than 102 / mm2. Therefore, the defect level on the substrate surface of the CVD growth substrate or below the surface can be minimized by carefully preparing the substrate. Because when each substrate is completed, each stage may affect the density of defects that fall inside the material that will eventually form the surface of the substrate, the manufacturing in this case includes any kind of In the case of diamonds) or synthetic (in the case of synthetic materials) materials. The special 10 processing steps may include conventional diamond manufacturing methods, such as: mechanical grinding, lapping and polishing (especially applicable to low defect levels in this application), and less commonly used techniques, such as: Laser manufacturing or ion implantation and stripping technology, chemical / mechanical polishing, and liquid and plasma compound manufacturing technology. In addition, the surface Rq (a flat surface cross-section measured with a styius 15 profilometer, preferably a length greater than 0.008 mm) should be minimized and etched by plasma The previous typical value is no more than a few nanometers (that is, less than 10 nanometers). 20

A special method for reducing the surface damage of the substrate comprises a plasma etching in situ on the surface of the crystals of the raw diamond. Theoretically, this rhyme does not need to be grown in situ or immediately afterwards, but in situ can achieve the highest benefit because it can avoid any risk of further physical damage or chemical pollution. When the crystal growth is also a plasma-based method, the 'origin engraving' is usually the most convenient. Plasma can be used similar to deposition or diamond growth, but does not use any carbon source 20 20, description of the invention gas and usually at a slightly lower temperature, 俾 to produce better etch rate control. For example, it can be composed of one or more of the following: (0) An oxygen etching method, which mainly uses hydrogen, optionally has a small amount of argon, and requires a small amount of 02. Typical oxygen etching conditions are 50-450 x 102 Pa, a gas containing the last name with an oxygen content of 4%, an argon content of 0-30%, and a balanced hydrogen, all percentages are by volume, with a base of 600_11〇 (rc Material temperature (more typically 800 ° C) and a typical duration of 3 to 60 minutes. (Ii) a hydrogen etching method similar to rhenium, but containing no oxygen. (In) selective for etching The method, but not solely argon, hydrogen and oxygen can also be used, for example: halogen, other inert gases or nitrogen are used. The etching method is typically etched by an oxygen, followed by a hydrogen etch, Then directly move into the synthesis by introducing a carbon source gas. The etching time / temperature can be selected so that the damage left on the surface by manufacturing can be removed, but does not form a highly rough surface, and there is no extensive Etching of elongational defects (for example: disl0cation across the surface), and thereby creating deep recesses. Since etching is aggressive, these stages are especially important for the design of the composition grooves of their components And material selection, so that no material is transferred into the gas phase or the surface of the substrate by the plasma. The hydrogen etching followed by the method of oxygen I insect engraving is less crystalline defects caused by the angular wear caused by the residual oxygen. Specificity, which will attack such defects invasively and provide _ a kind of flatter, more suitable for crystal growth. The surface or surface of the diamond substrate on which CVD diamond is grown is preferably 200416197 玖, description of the invention { 100} {110 丨, {113}, or {111} surface. Subject to the manufacturing method, the actual orientation of the U-port surface may differ from these theoretical orientations by as much as 5 degrees, and in some cases may reach 10 degrees. It affects the reproducibility less than desired. It is also important in the method of the present invention to appropriately control the impurity content in the ring 5 of the CVD growth. More specifically, the diamond growth must occur in a solid shell. S pollutants in the air, and The deliberately added boron (and if nitrogen is used) is appropriately controlled. The boron and nitrogen dopant concentration to be controlled depends on the embodiment ', but typically needs to be more than 20% stable, more typically it needs to be more than 1 〇%, even more typically, it needs to be more than stable. This type of control must carefully control the nitrogen impurities of the source gas, because nitrogen is a common pollutant. In order to achieve this degree of control, the source gas must be carefully added before nitrogen is added. The level of nitrogen in the gas is usually maintained below 500 ppb (based on the molecular weight of the total gas volume) in the gas phase, preferably below 300 ppb, more preferably below 100 ppb. The absolute and relative nitrogen 15 (or boron) concentration in the phase as low as Xuan Shuaichong requires precise monitoring equipment, such as gas chromatography to achieve it. An example of this method is described below: Standard gas chromatography (GC) involves using a narrow-hole sample line optimized for maximum flow rate and minimum dead volume, and from the point of interest A gas sample stream is drawn and then passed through the GC sample coil before being passed to waste 20. The GC sample coil is a piece of tubing surrounded by a fixed and known volume (for standard atmospheric pressure injection, typically 1 cm3), which can be transferred into the injection gas chromatography column from the position where the sample is located. Carrier gas (high purity helium) line. This allows a known volume of gas sample to be placed into the gas stream flowing into the column; in this technique, the process is called sample injection. η sample injection is through the carrier gas through the first GC tube (filled with a molecular filter optimized for the separation of simple inorganic gases), and then knife-by-knife, but high-concentration original gas (such as · · &Amp;, chlorine) will cause the full separation of the 5 official column to be saturated (for example: II gas lag &amp; (nitrogen diffic '. Then the part flowing out of the &quot; solid pipe column is injected into the second pipe column, This is to prevent most of the other gases from being passed into the second column, to avoid saturation of the column and to completely separate the target gas (nitrogen NO. This step is called "heart-cutting") 10 The output flow of the second column can be detected by an exhaust ionization detector (DID) to increase the leakage and release of carrier gas through the carrier gas caused by the presence of samples. The chemical structure can be determined by these The gas residence time corrected by the standard gas mixture is used for identification. The response of this DID is linear within 5 times the order and it is calibrated using a specially calibrated gas mixture15, which is typically at 1 °. Within the range of 4〇PPm The weight analysis method was later used to verify by the supplier. The linear relationship of the DID can be verified by careful dilution tests. This known technique of gas chromatography has been further improved. One step modification, It was developed for this application as follows: The method analyzed in this case is typically operated at 20 50-500 X 102 Pa. Normal GC operation uses excess pressure to exceed the pressure of the source gas to drive the gas through the sample line. In this case The sample is driven by connecting a vacuum pump to the waste end of the pipeline, and the sample is drawn under air pressure. However, the pressure of the pipeline in the pipeline will cause the pipeline pressure to decrease significantly. It affects the correction and the sensitivity of the invention description. Therefore, a valve is placed between the sample coil and the vacuum pump, which is closed within a short period of time before the sample injection, so that the sample cr port is closed. The pressure of the coil can be stabilized and measured with a pressure gauge. To ensure that a sufficient amount of sample gas is injected, the volume of the sample coil is increased to about 5 to 5 cm. Depending on the design of the sample line, this technique can be effectively operated at pressures as low as about 70 X 102Pa. The calibration of the GC can depend on the volume of the sample injected, and can be analyzed by simultaneous analysis. The supply and sample use the same pressure-corrected GC to obtain the highest accuracy. Very high standards of vacuum and gas operation must be observed to ensure that the measurement is accurate. 10 The sampling point can fall: upstream of the synthesis tank (for qualitative purposes) Input gas), reside in the tank (to characterize the environment in the tank), or downstream of the tank. Typically, diboron (B2H6) is added to the process. The deletion (B) uses a correction and is called 1 〇 〇ppm diborane (B2H6) mixed with Ha to simplify the control, the same nitrogen (NO to be added to the process of nitrogen is using 15 kinds of branches and is called 100pPm nitrogen H2 (N2 ) To simplify control. The added boron (B) and nitrogen (N) are expressed in ppm, which is calculated as [B2H6] / [all gases], where [B ^ 6] represents diborane (B2h6) Molar number, and [all gases] represents the mole numbers of all existing gases), which is similarly calculated as [N2] / [all gases] for nitrogen (n2). 20 The source gas can be any of the materials known in the art and containing carbonaceous materials which can dissociate to produce free radicals or other reactive species. The gas mixture will also typically contain hydrogen or a halogen suitable for providing atomic form. The dissociation of the source gas is preferably carried out in a reaction using microwave energy, 24 200416197, an invention demonstrator (examples of which are known in the art). However, the transfer of any impurities from the reactor should be minimized. A microwave system can be used to break the security deposit and place it in a distance other than the diamond H substrate surface φ and its base (made of substrate). An example of a base material is m, more carbon cut. An example of a preferred reaction vessel material is: stainless steel, aluminum, copper, gold, and platinum. Should use a kind of high electric power density that can generate high microwave power (typically 3 shoulder kilowatts (please) for 25 sides with a substrate carrier) and high gas pressure (50-500 X 102 Pa, compared with It is preferably 1045 × 10 2 pa). 10

Under the above conditions, a thick, high-quality CVD diamond layer can be manufactured, which has an extremely high flow charge carrier and has a shape that is most suitable for making these uniform for commercial products. Big volume. Hereinafter, embodiments of the present invention will be described. 15 Example 1

The substrate suitable for synthesizing the single crystal CVD diamond of the present invention can be prepared as follows: ⑴ The best raw materials (la-type natural gemstones and Ib-type high-pressure high-temperature (HPHT) gemstones) are selected by microscopic examination and birefringent images to identify the substrate. It is free of spots and impurities. 20 (丨 丨) Laser cutting, lapping, and polishing to minimize surface flaws' A display plasma etching method was used to determine the flaw levels that were introduced by processing. (iii) After optimization, the substrate can be manufactured according to conventional practices. The density of defects that can be measured by a display plasma etching method is mainly 25 200416197. The description of the invention depends on the material, and Less than 5 x 103 / mm2 'and usually less than ιOM2 / mm. A base material is prepared by this method, and thereafter used in a subsequent synthesis method. A high-temperature / high-pressure synthesized la-type diamond is grown under a high-pressure compaction 5 and the above method is used to minimize substrate defects, so as to form a size of 7.65 mm X 8.25 mm2 and a thickness of 0.54 mm. Polished plates with {100} on one side. The surface roughness Rq at this stage is less than. The substrate is placed on a tungsten substrate using a high-temperature copper-zinc alloy weld. It is introduced into a reactor and starts a plasma 10 and crystal growth cycle as described above: 1) The 2.45GHz reactor is pre-adjusted with a pure machine equipped to reduce the inhabitation in the feed gas flow. Desired pollutants, so that it is lower than 80ppb 〇2) at a substrate temperature of 270 X 102 Pa and a 753 ° C, using 15 15/75 / 6〇SCCm (standard cubic meters per second) Oxygen / Argon / Hydrogen (〇2 / Al / H2) to perform an in-situ oxygen plasma etching. 3) This can remove oxygen from the gas stream at a temperature of 758 (within 10 minutes) and move into a hydrogen etch without interference. 4) This is a process of adding crystals by adding a carbon source (cH4 in this example) and a dopant gas 20 body. In this example, the flow of methane (CH4) in the gas phase is 30 Sccm. Diborane (B # 6) is used as a source of boron dopants. The diborane (B ^ 6) gas concentration was 1.4 ppm. The temperature is 780 ° C. 5) When the growth phase is completed, remove the substrate from the reactor, and then remove the Cvd drill grown on one of the above-mentioned low defect density surfaces from the substrate. 6) The layer is subsequently flattened to produce a uniform boron doped layer with a thickness of <50.00 mm and a side dimension of about 5 x 5 mm2 and a thickness of 73 5 µm. 7) The layer identified as CD-1 was cleaned and its surface was cleaned with a spray of oxygen (02), and then its mobility was tested using the Hall technique. Measured at 300K is 360cm2 / Vs and 440K is 185

cm2 / VS 〇 This data is consistent with the T_L: dependence predicted by an acoustic phonon scattering pattern. 8) Using a secondary ion mass spectrometer (SIMS) to analyze this layer, it can be determined that the side with uniformity (B) has a total concentration of 6 · 2 X 1018 atoms / cm3. 9) The carrier technique was used to test the carrier concentration at 4.5K 10 5 at 200K, 4 X 1015 at 300K, and 1.6 X 1017 at 500K. The upper limit of the mobility of the carrier concentration at 4K 1015 at 300K calculated according to function (1) is 163 cm2 / Vs', and the measured value is 360 cm2 / Vs. Therefore, the G factor (defined as function 1 above) shown by 15 is higher than that of materials of conventional skill

twenty two. Example 2 The method described in Example 1 was repeated with the following changed conditions: 1) The polished high pressure and high temperature (HPHT) substrate was 500 μm thick and all 20 surfaces were {100} 5 x 5 mm squares. 2) At 333 X 10 2 Pa and a substrate temperature of 800 ° C, use in situ oxygen / argon / hydrogen (CVAr / H2) at 15/75/600 sccm (standard cubic centimeters per second) (In situ) oxygen plasma etching. 3) Followed by a 30-minute hydrogen etching, in which oxygen 27 200416197 玖, description of the invention (〇2) was removed from the gas flow, and the temperature was maintained at 810 ° C. 4) The growth of crystals is by adding 36 sccm of methane (CH4) gas stream and generating diborane (B2H6) and nitrogen (N2) gas streams with gas concentrations of 0.05 and 7 ppm, respectively. The temperature is 812 ° C. 5 5) When the growth phase is completed, the substrate is removed from the reactor, and then the CVD diamond layer body is removed from the substrate. 6) The layered body that was identified as CD-2 was flattened to produce a layered body with a thickness of 410 μηι with a single side with a size of &lt; 100 &gt; 10 7) SIMS was used to analyze the layered body. A series of measurements showed that the layered body had a concentration of 6.1 X 1018 atoms / cm3 on one side. The SIMS spectrum of the deleted (B) concentration shows that there is no concentration difference under the resolution of the spectrum. The spectrum has a lateral space resolution of less than 30mm and a measurement sensitivity level of more than 10%. The measured nitrogen concentrations were all lower than 5 x 105 cells / cm3. 8) The layer identified as CD-2 was cleaned and its surface was sprayed with oxygen (02) to remove its surface 'and tested for its mobility and carrier concentration. The carrier concentration was measured to be more than 4.5 x 1013, and the mobility was measured to be more than 2.5 x 103 cm2 / Vs, yielding a G value of about 1.5. 2 0 9) CD-2 can be further characterized by the following data: (i) its CL spectrum shows free and bound excitation, and has no other characteristics. (ii) Electron magnetic resonance spectroscopy (EPR) shows that there is no electrically neutral replacement gas and only a weak line with g = 2.0028. 28 200416197 (ii) Description of the invention (iii) The spectrum shows that it has an approximate theoretical penetration except for the characteristic absorption related to an uncompensated boron concentration of 6.5 X 10 6 atoms / cm3. (iv) The X-ray rocking curve shows that the angular distribution of the sample is less than 10 arc sec. 5 (v) The Raman spectrum shows that the full width at half maximum (FWHM) of a line width is about 2 cm_1. Example 3

The method described in Example 1 was repeated with the following changed conditions: Argon (Ar) 75sccm, Hydrogen (H2) 600sccm, Methane (CH4) 30 10 seem, 330 x 102 Pa, 795 ° C, 4.4kW, B The borane (B2H6) and nitrogen (N2) gas concentrations were 15 and 0.5 ppm, respectively. Thereafter, both sides of the CVD layer body having a thickness of 300 µm were appropriately processed and analyzed. A SIMS spectrum on the top surface shows a boron concentration of 1.75 X 1018 15 atoms / cm3, and an average SIMS concentration on the bottom surface is 1.98 X 1018 atoms

/ cm3 〇 Example 4 The method described in Example 1 was repeated under the following changed conditions: Argon (Ar) 50sccm, Hydrogen (H2) 600sccm, Methane (CH4) 40 20 seem, 330 x 102 Pa, 795 ° C, 4.4 kW, diborane (B2H6) and nitrogen (N2) gas concentrations were 0.05 and 0.7 ppm, respectively. Thereafter, both sides of the C VD layer body having a thickness of 113 μm were appropriately processed and analyzed. A SIMS map on the top surface is measured from a 0.5mm groove depth within an area of 2mm X 4.5mm and a 1mm depression within an area of 5mm X 6mm. 29 200416197 发明 Description of the groove depth. The bottom data is measured from a 1mm groove depth. Therefore, the volume analyzed was 3.4 mm3. The measured average shed concentration on the top surface was 0.56, and the bottom surface was 0.52 ppm. Therefore, it is determined that the material has an average of 5 volume percentages within a specific concentration range is shown in Table 1; Table 1-SIMS concentration and distribution analyzed on a 1mm groove SIMS standard unit details surface volume boron concentration average ppm Top surface Bottom surface 0.54 1.0mm Groove 0.56 0.52 Value range% 100% -24% to + 23% -14% to + 16% -21% to + 27% (range 48%) 95% -17% to + 20% -14% to + 11% -17% to + 18% (range 35%) 85% -11% to + 14% -11% to + 11% -15% to + 13% (range 28%) 70%- 90 / 〇 to + 9% -7% to + 9% 9% to + 10% (range 28%)

Therefore, Table 1 shows that 100% of the boron measurement falls within a total range of 47% of the top surface of the sample and a total range of 30% of the bottom surface of the sample.

10 and 30% of the binding volume of the two main surfaces when combined analysis. Similarly, 70% of these measurements fall within the range of 19% of the two surface mergers. The nitrogen concentration measured in this layer is less than 0.06 ppm, and this upper limit is set to the sensitivity of the measurement conditions used. The bottom surface of the sample was further analyzed using the MonoCL system to analyze 15 free-emitting free exciton scattering (FE) and excited-excitation (BE) intensities to obtain a 6 x 6 matrix (36 data points) on the 1 mm groove The results are shown in Table 2. 30 200416197 发明, Description of the invention Table 2- Distribution of FE and BE measurements Measurements% of total range (% of average value) Top and bottom BE FE BE / FE BE FE BE / FE 100% 41 34 31 95 % 39 29 28 90% 25 18 25 85% 20 15 24 70% 14 12 17

Therefore, the free excitation measured by 90% of boron (B) on the top surface of the sample falls within the average 25% range, the free excitation is 25%, the combined excitation is 5 and 18%, and the BE / FE ratio Is falling at 25%. Example 5 Crystals were grown into a layered body by the method described in Example 4. Thereafter, both sides of the CVD layer having a thickness of 233 μm were appropriately processed and analyzed. The volume analyzed was 7.0 mm3. 10 Determine the butterfly concentration on the top surface to be 0.34 ppm and the bottom surface to be 0.29 ppm.

Both were 0.32 ppm. Therefore, it was determined that the material had a volume percentage with an average value in a specific concentration range. Table 3 is shown in Table 3:% of the volume of the distribution layer measured by boron (B) measurement in SIMS. Binding and boron (B) concentration were measured. Upper limit of the lower limit of the distribution 100% -22% + 24% 46% 95% -21% + 19% 40% 85% -13% + 13% 26% 70% -10% + 9% 19% 15 In this layer The measured nitrogen concentration is less than 0.03 ppm. The upper limit is 31 200416197. The invention description is set to the sensitivity of the measurement conditions used. The top and bottom surfaces of this sample were further analyzed by the MONCL system for free excited emission free exciton scattering (FE) and combined excited emission (BE) intensity to obtain a 6 X 6 matrix (36 data points) The data on the 1mm groove, 5 The results are shown in Table 4. Table 4- Distribution of FE and BE measurements% of total range values (one of the average top surface bottom surface BE FE BE / FE BE FE BE / FE 100% 20 14 26 19 29 32 95% 16] 12 22 17 24 21 90% 13 11 18 14 21 17 85% 11 9 17 13 14 '14 70% 10 8 14 11 9 12 The top and bottom surfaces are used as the two main surfaces, which shows 90% free and combined excitation The BE and FE ratios substantially fall within a distribution range of about 10 to 30% of the average value. Example 6 Crystals were grown into a layer by the method described in Example 4. Thereafter, the thickness was appropriately processed and analyzed to be 538 μϊΏ. Both sides of the CVD layer. The volume analyzed was 16.1 mm3. 15 The boron concentration on the top surface was determined to be 0.52 PPm, the bottom surface was 0,34 ppm, and the average was 0.43 PPm. Therefore, it was determined that 70% of the volume of the layer was Within the range of -23.3 to +23.4 of the average value, it is 46.7% of the full range. Thereafter, the SIMS pattern of boron (B) was overlaid on the long crystal plane with a resolution of less than 30 μιη to further show the locality Boron is homogenous, and the result is 32 200416197. The description of the invention is shown in the following table 5. Analysis of elements other than carbon shows no The quality exceeds the detection limit of 0.5 ppm. The nitrogen concentration measured in this layer is less than 0.03 ppm, and this upper limit is set to the sensitivity of the measurement conditions used. 5 The top and bottom surfaces of the sample It is further used MonoCL system in SEM

To analyze the free exciton free exciton scattering (FE) and the combined excitation emission (BE) intensity, the data on the imm groove of a 6 X 6 matrix (36 data points) were obtained. The results are shown in Table 5.

Table 5-Boron (B) concentration and the distribution of FE and BE measurement% of total range (% of average value) Top surface bottom surface boron concentration * 1 Boron concentration * 2 BE FE BE / FE Boron concentration * 2 BE FE BE / FE 100% 25 30 41 33 30 29 20 13 25 95% 24 24 39 28 27 25 16 12 22 90% 25 18 24 13 10 18 85% 15 22 19 15 23 16 11 8 17 70% 12 14 14 12 17 9 9 8 13 10 mSIMS, resolution &lt; 30μπι * 2SIMS, resolution &lt; 50μηι This layer also uses infrared (IR) absorption spectrum to measure an area of 5 x 5mm (36 data points) Difference in uncompensated shed with 1mm groove. 15% of 90% measurements fall within a range that is approximately 34% of the average. The Raman / optical cold light spectrum was measured using a 514nm argon ion laser cold light at 77K. The spectrum is characterized by a diamond Raman spectrum line of approximately 133201 ^ 1, and the full width at half maximum value (FWHM) of the spectrum line is 1.6 cm_1. Detecting its zero phonon spectral lines at 575 and 637nm, it shows that the ratio of the peak intensity to the peak intensity of Laman 20 is 1: 1000. 33 200416197 (ii) Description of the invention Example 7 A crystal was grown into a layered body by the method described in Example 4. Thereafter, a layer having a thickness of 818 μm was appropriately processed. The infrared (IR) absorption spectrum was used to measure the difference in an uncompensated shed with a 1mm groove on an area of 5 X 5tnm (36 data points). 5 90% of the measurements all fall within a range of about 13% of the average. [Schematic Briefing Note 3 (none)

[Representative symbol table for main components of circle type] (none)

34

Claims (1)

200416197 Patent application scope: A single crystal boron doped diamond layer body manufactured by chemical vapor deposition (CVD). The total concentration of boron is given by a lateral resolution of less than 50 (1111) at each measurement point. It is measured to have a homogeneity of a majority of the layer differences less than 50%. The majority of the layers means at least 5 70 ° / ° of the total volume of the layer, and the layer has at least one of the following characteristics (i) -(in): (i) the layer is formed from a single crystal growth tank, ii) the thickness of the layer is more than 100 μm, and (ii) the volume of the layer is more than 1 mm3. The diamond layer of item 丨, wherein the difference between the majority of the volume 10 is less than 20%. 3. If the diamond layer of item 1 or 2 of the patent application scope, the difference is that each measurement point is less than 30. The lateral resolution is measured. 4. The diamond layer body according to any one of the aforementioned patent applications, wherein a part of the volume of the layer body 15 contains a type higher than 1 X 1014 atoms / cm3 and lower than i χ 102G. Uncompensated boron concentration in atom / cm3. The diamond layer of any one of clauses, wherein a majority of the volume of the layer contains an uncompensated boron concentration higher than 1 X 1015 atoms W and lower than 2 X 10 atoms / cm3. Please claim the diamond layer of any of the scope of item 丨 · 3, wherein most of the volume of the layer contains an uncompensated boron concentration higher than 5 x 1015 atoms W and lower than 2 x 1018 atoms / cm3. . For example, the diamond layer body in any of the 4 patent scopes mentioned above has a kind of gate at 300KT $ Measure &lt; hole movement rate is more than 35 200416197, patent application scope Mh = GX 2.1 X 1〇10 / (Nh0 · 52) When Nh is less than or equal to 8 X 1015 atoms / cm3 (function 1) X 1 X 1018 / Nh When Nh is greater than 8 X 1015 atoms / cm3 (function 2) where Nh is the hole concentration and G Is a value greater than. 8. The diamond layer of item 7 in the scope of patent application, where 0 is a value greater than 1.4. 109. The diamond layer body according to item 7 of the patent application scope, wherein G is a value greater than 17. 10. For the diamond layer of item 7 of the patent application, where g is a value greater than 2. 11. The diamond layer body according to any one of the foregoing patent applications, which is weak or absent at 575nm and 637nm related to the nitrogen-space 15-gap (N-V) core. Cold light characteristics. 12. If the diamond layer of any one of the scope of application patent No. 丨 _10, wherein the integral of the zero phonon spectrum of the nitrogen gap at 575nm vs. 637nm peak measured at 77K with 514nm argon ion laser excitation The intensity is less than 20 times the integrated intensity of the Raman line of the diamond falling at 1332 cm · 1. 13. If the diamond layer body in the scope of patent application No. 12 in which the ratio is less than 1/100 〇14. If the diamond layer body in the scope of patent application No. 12 in which the ratio is lower 36 200416197 At 1/300. 15. The diamond layer body according to any one of the aforementioned patent applications, which has a Raman spectral line width at half maximum height (FWHM) measured at 300K under 5 14nm argon ion laser excitation is less than 4cm- 1. 5 16. The diamond layer of item 15 in the scope of patent application, wherein the FWHM of the Raman spectral line is less than 3 cm_1. 17. The diamond layer body of item 15 in the scope of patent application, wherein the width at half maximum width (卩 \\ ^] \ 4) of the Raman spectrum line is less than 2.5〇111 ". A diamond layer of one item, wherein the sampling frequency of the uncompensated boron concentration from a representative sample of the layer 10 is measured by a Fourier transform infrared spectrometer (FTIR), and its 90% measurement The difference is less than 50% of its average value. 19. If the diamond layer body according to any one of the M7 scope of the patent application, the sample is taken from the uncompensated deletion concentration of a representative sample. The distribution frequency 15 is measured by a Fourier transform infrared spectrometer (FTIR), and the difference between its 90 / ❶ measurement is less than the average of its percentage. 2 · As described in any of the patent application scopes Diamond layer, in which the sampling frequency from the representative sample of the layer combined with the distribution frequency of exciton scattering (BE) shows that the difference between its 90/0 measurement is less than 20 50% of its average. 2L If you apply for any of the items in the scope of patents 1-19 The layered body, in which the sampling frequency from the representative sample of the layered body combined with the distribution frequency of exciton scattering shows that the difference between 90% of its measurements is less than 30% of its average value. 37 200416197 Patent application scope 22. The diamond layer body according to any one of the foregoing patent applications, wherein the free exciton radiation free exciton scattering (FE) distribution frequency of the representative surface of the layer body or the layer body sampled, which The difference of 〇% measurement is less than 50% of its average value. The diamond layer of any one of claims 1-21 is claimed, in which any one of the representative surfaces of the layer or the layer The free exciton scattering (FE) distribution frequency of the sample, the amount of 90% 'of which has a difference of less than 300/0 of its average value. A diamond layer of one item, wherein the majority of the 10 minute volume represents more than 85% of the total volume. 25. The diamond layer of any one of items 1 to 23 in the scope of the patent application, most of which is in volume Represents more than 95% of the total volume. • As stated The diamond layer body of any one of the patent scopes, wherein the layer body is grown from a single crystal cell, which is a {100}, {110} '{⑴} or {111} cell. Month' J The diamond layer body of any of the patent scopes mentioned above has a thickness of more than 500 μm. • The diamond layer body of any of the patent scopes of the patent application has a volume of more than 3mm3 〇2 0 2 9 The mouth is controlled by ▲ ° Please request the diamond layer body of any of the patent scope items 1-27, whose volume exceeds 10mm3. 30. As described above, the diamond layer body of any patent scope, which also contains nitrogen as an impurity . 3 1 If it is claimed as the diamond layer body in item 30 of the patent scope, the nitrogen concentration does not exceed 38 200416197. The scope of the patent application exceeds one fifth of the boron concentration. The nitrogen concentration contained in it 32. For example, the diamond layer body in the scope of patent application No. 30 does not exceed 1/50 of the boron concentration. 33. A diamond body, in which the diamond layer as described in any one of the foregoing patent claims forms a thin layer or region thereof. 34. If the main body of the patent application scope is 30 ^^ or the wrong stone layer body according to any of the patent application scope items 1-32, it is in the form of a gem. 35.-A kind of element ’, which is made of the iron stone layer body such as any one of the scope of patent application item (3) or the diamond body as the patent application scope of item 0. 36. A method for manufacturing a single crystal boron-doped diamond layer, comprising the steps of: providing a diamond substrate having a surface substantially free of crystal defects, providing a source gas, the source gas comprising a boron Source, dissociating the source gas, and then allowing homogeneous epitaxial diamonds to grow on the surface without crystal defects. 37. The method of claim 36, wherein the single crystal boron doped diamond layer system is as defined in any of claims 1-32 of the scope of patent application. 38. The method of claim 36 or 37, wherein the nitrogen added to the source gas is in a form suitable for controlling the amount of formation by single crystal diamond growth. 39_ The method according to the scope of the patent application, wherein the nitrogen added to the source gas is higher than 0.5 ρρηι and less than 1000 ppm. 40. The method according to the scope of the patent application 38, wherein the addition to the source gas 39 200416197 The nitrogen in the scope of the patent application is higher than 1 ppm and less than 1000 ppm. To the source gas 41. If the method of the 38th scope of the patent application is applied, the nitrogen in the additive body is higher than 3 ppm and Less than 200ppm. The method of item, wherein the characteristic density remaining on the surface is low. 42. As shown in the patent application scope of any of the 36_41 diamond crystals, the defect-related surface is shown in 5 X 10 / mni2 〇43. The method according to any one of the 36th to 41st patent scope, wherein The surface engraved characteristic density associated with blemish on the surface of diamond crystals is lower than 102 / mm2. 44. The method of any one of items 36-43 in the scope of Shenyan's patent, wherein the surface of the diamond crystal is before the diamond crystal, and is first introduced to a plasma etching. 45. The method according to any one of items 36 to 44 of the scope of application for a patent, wherein the diamond is grown on a {i00}, {110}, {113}, or {111} surface. 46. The method according to any one of claims 38.45, wherein the source of boron 15 is diborane (β2η6). 47. For the diamond layer body in the scope of patent application, it refers to any embodiment and is substantially as described in this case. 48. The method of applying for the item in the patent scope refers to any embodiment and is substantially as described in the present case. 40 200416197 Lu, (1), the designated representative of this case is: Figure _ (2), the component representative symbols of this representative diagram are simply explained: (none) 柒 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention = (None) 4