WO2011078299A1 - 異種元素結合形成法 - Google Patents
異種元素結合形成法 Download PDFInfo
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- WO2011078299A1 WO2011078299A1 PCT/JP2010/073255 JP2010073255W WO2011078299A1 WO 2011078299 A1 WO2011078299 A1 WO 2011078299A1 JP 2010073255 W JP2010073255 W JP 2010073255W WO 2011078299 A1 WO2011078299 A1 WO 2011078299A1
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- C08J2383/16—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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Definitions
- the present invention relates to a technique for forming a dissimilar metal bond using a low-temperature atmospheric plasma jet, and in particular, a group 13 element or a group 15 element on a silicon film using poly and oligosilane compounds that can be formed by a coating method. This technique is useful for doping.
- Silicon semiconductor is a material that has been studied for a long time as a material for thin film transistors (TFTs) and solar cells.
- TFTs have a long history of investigation, and were proposed as current control elements by Lilianfeld et al. In 1930. In 1945, the operation of a thin-film vacuum-deposited silicon thin film was confirmed. This characteristic evaluation was considered by Bardeen et al., Leading to the idea that the electric field to the semiconductor surface due to the gate potential is shielded by the surface level and does not cause a substantial change of the surface carrier (Bardeen's model).
- bipolar transistors became active, and various discrete devices were developed. However, it became cheap and replaced the vacuum tube.
- TFTs made of silicon did not exhibit characteristics, and compound semiconductors such as CdS were used, and the characteristics were not stable at all.
- RCA improved the characteristics and in 1962 developed a TFT using a CdS thin film showing good characteristics.
- Westinghouse made and operated TFTs on Mylar (polyethylene terephthalate), Kapton (polyimide) and paper, which are also used in flexible displays. So far, II-VI compound semiconductors, tellurium (Te), etc. have been used as semiconductor materials.
- CdSe As a compound semiconductor, CdSe easily becomes a polycrystalline structure by a low temperature process such as vapor deposition, and its mobility is about 50 cm 2 / Vs, and at the same time, it has high ionic current and low off-current, which makes it a TFT material. Although it has been widely used, since it is a binary compound semiconductor, it inherently has problems such as stoichiometry and instability of transistor characteristics due to the contact state between the gate insulating film and the CdSe interface. .
- the (a-Si: H) film has excellent film uniformity, reproducibility, and fine workability in forming a large area thin film, and can be said to be a material suitable for a large area device.
- a-Si amorphous silicon
- the process can be performed at a relatively low temperature, and the resulting TFT can be operated with a high resistance material and a low voltage AC, so an LCD is used as a basic switch element. Yes.
- a plasma CVD method, a photo CVD method, a thermal CVD method, and a reactive sputtering method are known.
- a method of generating a reactant generated by a plasma reaction by forming an electron flow from a minus electrode to a plus electrode through a minute substance and inducing plasma on the surface of the minute substance based on a potential difference (see Patent Document 1) There is.
- a thin film formation method in which a reactive gas that is a material for a thin film is introduced into a reaction furnace, a voltage is applied between electrodes to generate plasma, decompose the reactive gas, and cause a chemical reaction to deposit a thin film on a substrate Patent Document 2.
- plasma CVD method plasma is generated by applying electrical energy to a Si-based material gas such as silane gas (SiH 4 ) to generate active radicals and ions, and a chemical reaction is performed in an active environment.
- This generated plasma has two temperatures, an electron temperature and a gas temperature, both of which are high temperature plasma, which is as high as tens of thousands of kelvins, and the electron temperature is as high as tens of thousands of kelvins, but the gas temperature is as low as room temperature to several hundred degrees Celsius.
- this low temperature plasma when used, a thin film can be formed while keeping the substrate temperature low, so the substrate must be raised to a temperature close to 1000 ° C. as in the conventional thermal CVD method.
- the generated active species reach the substrate surface mainly by diffusion, and are then formed into an a-Si thin film through processes such as adsorption, separation, extraction, insertion, and surface diffusion.
- the power used for plasma generation is direct current, radio wave, high frequency, microwave, etc., but the most frequently used is the high frequency in the 13.56 MHz band.
- electrodes are placed facing each other in a vacuum chamber, and the high voltage side electrode is connected to a high frequency power source via a dielectric or the like to become a cathode electrode. The other electrode is grounded together with the vacuum chamber and becomes an anode electrode.
- the excitation and decomposition reactions of SiH 4 occur actively in this region, and the thin film stacking speed is also high on the cathode side.
- the substrate on which the laminated film is formed is generally installed on the anode side.
- this installation method is also affected by ion bombardment, which is a drawback in the plasma CVD method. This impact effect becomes more prominent as the pressure is lower and the input power is higher.
- the generated active species collide and deactivate in the SiH 4 gas.
- SiH 3 is stable against the deactivation due to these collisions. That is, since SiH 3 has low reactivity, as long as there is no dangling bond on the growth surface, it cannot participate in network formation alone.
- the surface of the grown film is almost covered with hydrogen at a substrate temperature of 100 to 300 ° C., and SiH 3 that reaches the surface searches for a site where hydrogen is extracted while diffusing the surface. It becomes.
- Si atoms are arranged at sites that are more stable in terms of energy, and a dense amorphous film having a high degree of relaxation is formed.
- the diffusion coefficient of the reactive species is increased by the reaction at a high temperature (350 ° C. or higher), and a dangling bond generated by the thermal detachment of the surface-covered hydrogen is not generated by supplying a large amount of SiH 3.
- New low-defect film creation techniques have been developed, such as a method for incorporation into a film, supply of thermal energy to reaction-dominated species, and photoexcitation of the growth surface to promote surface diffusion.
- the growth / hydrogen plasma treatment repetition method (chemical annealing method) which tries to relax the amorphous structure which has not yet solidified several atomic layers from the growth surface with the help of atomic hydrogen, reduces the growth rate of the thin film
- a method has been proposed to give the necessary time. Thin films made by these methods are particularly useful for (a-Si: H) solar cells.
- the photo-CVD method is a general term for a method of decomposing SiH 4 using light energy directly (referred to as direct photo-CVD) or indirectly (referred to as mercury-sensitized or indirect photo-CVD). This is called the CVD method.
- direct photo-CVD direct photo-CVD
- mercury-sensitized or indirect photo-CVD indirect photo-CVD
- the CVD method it is considered that mild growth conditions can be obtained because the surface of the growth film is not subjected to high-energy ion species or electron impact.
- the mercury sensitization method it is said that SiH 3 reactive species having a large surface diffusion coefficient are selectively generated, and conditions suitable for forming a high-quality film can be achieved.
- the low deposition rate is a problem, but it is covered by using higher order silanes such as Si 2 H 6 and Si 3 H 8 with high decomposition efficiency instead of SiH 4 .
- the thin film is generally doped by a vapor phase doping method. Doping can be easily performed by reacting SiH 4 source while adding impurity gas such as PH 3 , AsH 3 (n-type), B 2 H 6 (p-type).
- impurity gas such as PH 3 , AsH 3 (n-type), B 2 H 6 (p-type).
- an amorphous silicon film can be obtained at a relatively low temperature (about 300 ° C.), and at the same time, by using SiH 4 and another mixed gas, these two types can be used on the solid surface or in the gas phase. It is possible to create bonds between different elements by reacting the above molecules.
- Polycrystalline silicon aims to reduce costs by reducing the cost of crystallization, which represents the majority of the raw material cost of single crystal silicon, and is mainly used for the substrate production process including the purity and crystallization of raw materials. It is an improvement.
- FIG. 1 there are three methods for producing a polycrystalline silicon wafer: an ingot slicing method and a sheet method according to the presence or absence of a substrate. A method as shown in FIG. 1 has been proposed for these three types. .
- the metal grade silicon impurity concentration of about 10-2
- the crystal grain size When making polycrystalline silicon, the first thing to consider is the crystal grain size. In particular, in solar cells, if the crystal grain size is larger than the film thickness, minority carriers that flow into the junction and effectively contribute to power generation become sufficiently larger than the flow to the grain boundary that shows a short carrier lifetime. This is because the influence of grain boundaries can be suppressed. In an actual silicon solar cell, a grain boundary of 50 ⁇ m or more is necessary. This crystal grain boundary largely depends on the manufacturing method and the film thickness, and is generally roughly classified into a liquid phase method and a gas phase method. The method shown in FIG. 1 corresponds to the liquid phase method.
- the ingot & slicing method is a method in which molten silicon is poured into a mold and cooled to create an ingot and slice it.
- Wacker's Silso and Crystal System's HEM Heat exchange method
- these liquid phase methods generally use silicon after melting, high temperature treatment is required and a large-scale apparatus is required.
- a silane gas and a dopant gas are mixed in an ultra-high vacuum chamber to form a silicon film on the substrate. Since a vacuum chamber is required, the substrate area is the chamber volume. There are problems such as being restricted to.
- dangling bonds formed during film formation combine with some impurity element during crystal growth to form an electronic state having energy corresponding to a forbidden band in single crystal silicon. This acts as a trap site or recombination center for minority carriers and generally shortens the device lifetime. In the plasma CVD method or the like, these dangling bonds must be inactivated by short-circuiting using hydrogen. This operation also needs to be performed in the CVD apparatus, and here too, there is a problem in the process such as the need for an ultra vacuum chamber.
- the present invention overcomes such drawbacks and provides a doping technique for forming a stable amorphous silicon film and a polycrystalline silicon film at a low temperature and simultaneously imparting conductivity in an atmospheric pressure environment.
- an introduced gas is allowed to flow between the inside of a discharge tube having a high voltage electrode attached to a metal tube or an insulator tube or between two flat plate electrodes having a high voltage electrode attached thereto.
- a high voltage at a low frequency molecules existing inside the discharge tube or between the plate electrodes are turned into plasma, and the plasma is converted to simple elements 2 contained in groups 4 to 15 of the periodic table.
- the elements included in Groups 4 to 15 of the Periodic Table are irradiated with two or more species, two or more compounds containing the element, or an irradiated body that is a combination of the simple substance and the compound.
- a method for producing a compound containing a bond between different elements of As a second aspect, the production method according to the first aspect, wherein the compound containing a heterogeneous element bond is a compound containing a heterogeneous element bond between elements included in Groups 13 to 15 of the periodic table,
- the first or second aspect is characterized by irradiating the irradiated body with the plasma or radicals of surrounding gas excited by the plasma and further irradiating the irradiated body with ultraviolet rays.
- the irradiated object includes two kinds selected from the group consisting of the element simple substance, the compound, a solution containing the element simple substance, a solution containing the compound, a gas of the element simple substance, and a gas of the compound.
- the manufacturing method according to any one of the first to fourth aspects As a sixth aspect, the irradiated object is a compound containing one element of a group 14 element, and the other element is a gas containing a single element contained in groups 4 to 15 or a compound containing the element.
- the irradiated object is a compound in which one type includes a group 14 element, and the other type includes a single group 13 element or a compound including the element, or a single group 15 element.
- a compound containing the element, and a single group 13 element or a compound containing the element or a group 15 element or a compound containing the element per 0.2 mole of the compound containing the group 14 element The production method according to any one of the first to sixth aspects, which is contained at a ratio of 10 mol
- the production method according to the first aspect wherein the compound containing a bond between different elements includes a Si—Si bond and a Si—B bond or a Si—P bond
- a compound containing a Group 14 element is represented by the formula (1): (In formula (1), n represents an integer of 2 to 40), a chain silane compound represented by formula (2): (In formula (2), h represents an integer of 3 to 10), a cyclic silane compound represented by formula (3): (In Formula (3), h represents an integer of 3 to 10), and Formula (4): (In the formula (4), m represents an integer of 6, 8, or 10)
- the sixth to eighth aspects which is at least one silane
- a simple substance of the group 15 element or a compound containing the element is represented by the formula (6):
- w represents an integer of 1 to 10
- u represents an integer of 0 to 12
- X represents a hydrogen atom or a monovalent organic group.
- the gas introduced into the discharge tube or between the flat plate electrodes is helium, neon, argon, krypton, xenon, nitrogen molecule, oxygen molecule, hydrogen molecule, carbon dioxide, nitrogen monoxide, nitrogen dioxide.
- the gas introduced into the discharge tube or between the plate electrodes is helium alone gas, or helium and hydrogen molecule, oxygen molecule, nitrogen molecule, carbon dioxide, carbon monoxide, fluorine molecule, and chlorine.
- the production method according to any one of the first to eleventh aspects, which is a mixed gas with at least one gas selected from the group consisting of molecules,
- a fourteenth aspect a structure in which the two metal or insulator plate electrodes face each other, a high voltage electrode is connected to one of them, and the other is connected to the ground without being connected to the ground, or connected to the ground electrode.
- gas is passed between both electrodes to convert molecules existing between the electrodes into plasma.
- the two metal or insulator plate electrodes are in a decompression vessel, and an introduced gas is allowed to flow after decompression, and a high voltage is applied at a low frequency under a low gas pressure so that molecules existing between the electrodes are removed.
- the manufacturing method according to any one of the first aspect to the fourteenth aspect characterized in that the plasma is generated.
- the discharge tube of the metal tube or the flat plate electrode of the metal is composed of a single element contained in Group 4 to Group 14 or a mixture containing the element.
- any one of the first to seventeenth aspects is characterized in that the power source used for plasma generation is a frequency of 10 Hz to 100 MHz and an output voltage of 1000 V to 30000 V, and plasma irradiation is performed at a low temperature. It is a manufacturing method as described in one.
- a stable amorphous silicon film and a polycrystalline silicon film can be formed at a low temperature, and at the same time, doping that imparts conductivity in an atmospheric pressure environment can be performed.
- the present invention relates to a technique for forming a dissimilar metal bond using a low-temperature atmospheric plasma jet, and in particular, a group 13 element or a group 15 element on a silicon film using an oligosilane compound that can be formed by a coating method.
- This is a useful technique for doping. That is, by controlling the state of ionized gas with high energy called plasma jet by gas pressure and electric field, the chemical reaction by plasma is controlled, and doping of different elements into the silicon thin film is performed at a lower temperature near atmospheric pressure. Is possible.
- a plasma in a non-equilibrium state having a high energy component which is low in temperature but rich in reactivity is generated at a pressure higher than the vapor pressure of the liquid, that is, at a pressure of about atmospheric pressure, for example,
- a pressure higher than the vapor pressure of the liquid that is, at a pressure of about atmospheric pressure
- hydrogen is desorbed and silicon and boron are directly bonded.
- the atmospheric pressure (atmospheric pressure) plasma is an atmospheric pressure process that does not require a vacuum, it can be continuously processed. Further, plasma can be generated using helium gas that is easily ionized.
- This technology is a technology for manufacturing solar cells, transistors, and various sensors based on silicon semiconductors in a low-temperature wet process under atmospheric pressure. Since it can be manufactured by a low-temperature process, it is useful as a device weight reduction and plasticization technology.
- FIG. 1 is a diagram showing the types of methods for producing polycrystalline silicon.
- FIG. 2 is a schematic view showing a thermal non-equilibrium atmospheric pressure plasma jet apparatus.
- FIG. 3 is a diagram showing an emission spectrum from plasma.
- FIG. 4 is a schematic diagram showing a plate electrode thermal non-equilibrium atmospheric pressure plasma apparatus.
- FIG. 5 is a diagram showing the analysis result by XPS of the Si—N bond by nitrogen doping to oligosilane.
- FIG. 6 is a diagram showing the analysis result by XPS of the Si—B bond by boron doping to oligosilane.
- FIG. 7 is a diagram showing voltage-current characteristics of boron-doped amorphous silicon.
- FIG. 1 is a diagram showing the types of methods for producing polycrystalline silicon.
- FIG. 2 is a schematic view showing a thermal non-equilibrium atmospheric pressure plasma jet apparatus.
- FIG. 3 is a diagram showing an emission spectrum from plasma.
- FIG. 4
- FIG. 8 is an ESR spectrum showing holes formed in a valence band derived from boron formed by plasma irradiation.
- FIG. 9 is a diagram showing an ESR spectrum showing holes formed in a valence band derived from boron formed by plasma irradiation.
- FIG. 10 is a diagram showing an ESR spectrum showing holes formed in a valence band derived from boron formed by plasma irradiation.
- FIG. 11 is an ESR spectrum showing holes formed in a valence band derived from boron formed by plasma irradiation.
- FIG. 12 is an ESR spectrum showing electrons formed in the vicinity of a phosphorus-derived conductor formed by plasma irradiation.
- a compound containing a heterogeneous element bond is produced by irradiating a metal or a semiconductor element or a compound thereof with a radical caused by plasma (ionized substance) and an ambient gas excited thereby.
- the compound containing the heterogeneous element bond includes the heterogeneous element bond between the Group 4 element and the Group 15 element of the periodic table, and further the heterogeneous element bond between the Group 13 element and the Group 15 element of the periodic table. Is included.
- the phrase “including a heterogeneous element bond” means comprising a homogeneous element bond and a heterogeneous element bond.
- a compound containing a heterogeneous element bond is a group 14 element doped with a group 13 element, and (group 13 element) / (group 14 element) is in the range of 1 ⁇ 10 ⁇ 1 to 1 ⁇ 10 ⁇ 6 .
- the total amount of hydrogen is about 15 atomic% to 25 atomic%.
- As the Group 14 element doped with the Group 15 element, (Group 15 element) / (Group 14 element) is 1 ⁇ 10 ⁇ 2 to 1 It is in the range of ⁇ 10 ⁇ 5 and the total hydrogen amount is about 15 atomic%.
- a compound including a heterogeneous element bond can include a combination of a Si—Si bond and a Si—B bond or a Si—P bond.
- the doping amount of boron and phosphorus is not limited, but boron-doped p-type a-Si: H can measure the amount of hydrogen in the film by the hydrogen thermal emission method and the infrared absorption method (Z. E. Smith, Glow-discharged Hydrogenated Amorphous Silicon, KTK / Kluwer, Tokyo, Boston, 1989, 127).
- (B) / (Si) is in the range of 1 ⁇ 10 ⁇ 1 to 1 ⁇ 10 ⁇ 6 and the total hydrogen amount is about 15 atomic% to 25 atomic%. Phosphorus can also be measured by the same method.
- (P) / (Si) is in the range of 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 ⁇ 5 and the total hydrogen amount is approximately 15 atomic%.
- Under atmospheric pressure indicates the pressure of the environment in which the plasma is ejected, and is not particularly limited.
- the atmospheric pressure at which the reaction is performed in the range of the vapor pressure of the solution to 10 atm or less, more preferably the atmosphere under reduced pressure, It is suitable without requiring a pressurizing device.
- the compound containing a heterogeneous element bond can be obtained as a film on the substrate by coating the substrate with two or more kinds of elemental elements or a compound thereof as an irradiated body and irradiating it with plasma.
- the irradiated body can be used in a form in which the element itself, the compound itself, a solution containing them, a gas of the element alone or a gas of the compound, or any combination thereof.
- the irradiated object can use a compound containing a Group 14 element as one of them and a gas as another.
- the irradiated body uses a single group 14 element or a compound containing the element as one of them, and a group 13 element or a group 15 element or a compound containing these elements as the other. Can be used.
- a group 13 element, a group 15 element or a compound containing these elements can be used as a gas.
- At least one silane compound selected from the group consisting of Formula (1), Formula (2), Formula (3), and Formula (4) can be used.
- Formula (1) is a chain silane compound (including linear and branched silane compounds), and n is an integer of 2 to 40 or 2 to 30.
- Formula (2) and Formula (3) are cyclic silane compounds, and h is an integer of 3 to 10.
- Formula (4) is a cage-like silane compound, and m is 6, 8, or 10.
- the silane compound can be obtained by the following reaction.
- Cp represents a cyclopentadienyl group
- Ph represents a phenyl group
- the said silane compound can be obtained by the following reaction as another method.
- the above Ph represents a phenyl group.
- Formula (5) is mentioned as a single group 13 element or a compound containing the element.
- i is an integer of 1 to 10
- j is a boron component represented by an integer of 0 to 12. When j is zero, it is boron alone. When j is 1 to 12, it is borohydride (borane). Examples include monoborane (BH 3 ), diborane (B 2 H 6 ), tetraborane (B 4 H 10 ), and decaborane (B 10 H 14 ).
- gallium, indium, or a compound thereof can be used as a single group 13 element or a compound containing the element.
- Formula (6) is mentioned as a simple substance of a group 15 element, or a compound containing the element.
- w is an integer of 1 to 10
- u is a phosphorus simple substance or a phosphorus-containing compound represented by an integer of 0 to 12.
- u is zero, it is phosphorus alone.
- u is 1 to 12, it is phosphorus hydride.
- the simple phosphorus include white phosphorus, red phosphorus, yellow phosphorus, black phosphorus, and examples of the compound include phosphine (PH 3 ).
- nitrogen gas, nitrogen-containing compounds, arsenic, and arsenic-containing compounds can be used as the group 15 element simple substance or a compound thereof.
- nitrogen-containing compounds examples include amines, nitric acid, diazo compounds and the like.
- An example of the arsenic-containing compound is arsenic hydride.
- a single group 13 element or a compound thereof or a single group 15 element or a compound thereof is used in an amount of 0.2 to 10 mol, preferably 1 to 5 mol, per 1 mol of a compound containing a Group 14 element. Can do.
- a high voltage is applied at a low frequency while flowing a gas in a discharge tube in which a high voltage electrode is attached to a metal or insulator tube under atmospheric pressure (near atmospheric pressure). ) And irradiating the generated plasma to a metal or a compound to be a semiconductor or a solution thereof, a metal thin film can be formed.
- a metal tube is used as the electrode, only the high voltage electrode is connected to the metal tube, and the ground is the atmosphere (FIG. 2b).
- an earth can be attached before and after the high-voltage electrode (the distance is not in contact with the arc discharge), but the atmosphere can be grounded like a metal tube.
- An AC high voltage power source is used as a power source necessary for generating plasma.
- the alternating current indicates 10 Hz to 100 MHz, preferably 50 Hz to 100 kHz, more preferably 5 kHz to 20 kHz.
- the AC voltage can generate plasma in the range of 1000V to 30000V, preferably 1000V to 20000V, more preferably 5000V to 8000V.
- the material of the nozzle part used for plasma emission is composed of a single element included in groups 4 to 14 of the periodic table or a mixture containing the element, and a high voltage electrode is connected to this, and the ground side is used as the atmosphere. It is possible to use ionized gas and radical gas generated by applying a low-frequency high voltage while flowing. Although it does not specifically limit as an electrode material, for example, the gas flow path is formed, such as aluminum (pipe), stainless steel (pipe), copper (pipe), iron (pipe), and true casting (pipe) as a metal. Either a metal tube discharge tube or a metal electrode can be used.
- the discharge tube of the insulator tube or the electrode of the insulator is not particularly limited as a plastic, for example, but as a general-purpose plastic, polyethylene (high density polyethylene, medium density polyethylene, low density polyethylene), polypropylene, poly Examples include vinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, acrylonitrile butadiene styrene resin (ABS resin), acrylonitrile styrene resin (AS resin), acrylic resin, and polytetrafluoroethylene.
- the engineering plastic is not particularly limited.
- polyamide polyamide, nylon, polyacetal, polycarbonate, modified polyphenylene ether (m-PPE, modified PPE), polybutylene terephthalate, polyethylene terephthalate, polyethylene terephthalate glass resin (PET).
- m-PPE modified polyphenylene ether
- PET polyethylene terephthalate glass resin
- FRP glass fiber reinforced polyethylene terephthalate
- the super engineering plastic is not particularly limited, and examples thereof include polyphenylene sulfide, polysulfone, polyether sulfone, amorphous polyarylate, liquid crystal polyester, polyether ether ketone, polyamideimide, polyimide, and polyamide.
- an inorganic ceramic material can be used as an insulator tube or an insulating electrode.
- these include, but are not limited to, glass, silicon, zirconia, ceramics, alumina, titania, silicon carbide, silicon nitride, and the like.
- the plasma generated under the above conditions is used as a reactive species, but the gas introduced as the plasma generating gas inside the discharge tube or between the flat plate electrodes is a group 18 element (helium, neon, argon, krypton, xenon), At least one gas selected from the group consisting of nitrogen, oxygen, hydrogen, carbon dioxide, nitrogen monoxide, nitrogen dioxide, ammonia, halogen, hydrogen halide, sulfur disulfide, hydrogen sulfide, and water vapor is used. Moreover, it is possible to use helium alone gas or a mixed gas of helium and at least one gas selected from the group consisting of hydrogen, oxygen, nitrogen, carbon dioxide gas, carbon monoxide, fluorine, and chlorine.
- helium alone gas or a mixed gas of helium at least one gas selected from the group consisting of hydrogen, oxygen, nitrogen, carbon dioxide gas, carbon monoxide, fluorine, and chlorine.
- the mixed gas is 10 volumes or less, preferably 0.1 volumes of at least one gas selected from the group consisting of hydrogen, oxygen, nitrogen, carbon dioxide gas, carbon monoxide, fluorine, and chlorine with respect to 1 volume of helium. In the following, it can be more preferably 0.001 volume or less.
- the mixed gas does not need to be two kinds, and can be used by mixing three or more kinds of gases.
- the state of the plasma generated by mixing the gas and the radical that is the secondary product thereof can be changed, and this can be observed in the emission spectrum of the plasma.
- the ionization energy of helium excites nitrogen molecules, thereby extracting energy corresponding to ultraviolet light (see FIG. 3).
- This ultraviolet light is known to cut and cyclize the Si—Si bond of oligosilane or polysilane, which will be described later, and can be used to control the solubility of these silane compounds in a solvent and to form a network.
- Helium gas is commonly used because it is easy to produce stable plasma in the atmosphere.
- the flow rate of the gas used is a factor affecting the plasma parameters, but generally the flow rate is 1 ml / second or more, and can be used in the range of 1000 ml / second or less. Preferably, it can be used at 10 ml / second or more and 500 ml / second or less, more preferably 30 ml / second or more and 100 ml / second or less.
- the above silane compound is dissolved in a hydrocarbon solvent, and the thin film formed using this solvent is directly irradiated with plasma.
- a Si—C bond can be formed.
- the metal to be metalized by the reduction reaction by helium plasma is not particularly limited, but gold, platinum, silver, niobium, tantalum, nickel chloride is dissolved in the silane compound and formed using this solvent.
- a bond between silicon and a different element eg, gold, platinum, silver, niobium, tantalum, nickel
- a metal compound having an organic ligand can be used as a raw material.
- the central metal atom of the complex in which the metal is deposited by the reduction reaction there is a metal element in which the metal is included in Groups 4 to 15 of the periodic table, or Groups 4 to 14 of the periodic table, but is particularly limited.
- gold, silver, copper, palladium, rhodium, gadolinium and the like are preferable.
- compound particles such as metal oxides and nitrides by using two or more types of complexes or by using a plasma gas mixed with a gas other than helium. Is possible.
- organic complex examples include, but are not limited to, for example, a carbonyl ligand, a ⁇ acid ligand that reduces the electron density at the metal center through a d ⁇ -p ⁇ bond, a carbene ligand, an olefin, and an acetylene ligand. Etc. These complexes can be used in combination of several kinds.
- Two metal or insulator plate electrodes face each other and one side is connected to a high-voltage electrode, and the other is connected to the ground without connecting to the ground, or connected to the ground electrode. And plasma can be used. Then, there are two metal or insulator plate electrodes in the decompression vessel, and after introduction of the introduced gas, the introduced gas is flowed, and a high voltage is applied at a low frequency under a low gas pressure to make the introduced gas into plasma. .
- the plasma irradiation apparatus does not need to be a plasma jet emitted from a pencil-shaped nozzle in particular, and an AC electric field is applied to two opposed flat plate electrodes, and a gas that can become a plasma gas in this gap (particularly, it is not limited) It is possible to generate a stable atmospheric pressure plasma by flowing helium gas or the like, and to process the substrate by allowing the processing substrate to stand in this gap (FIG. 4).
- B 2 H 6 or PH 3 is introduced into the mixed gas, and the silane compound thin film is irradiated while being released into the helium ionized gas, so that it is easy at atmospheric pressure. It is possible to dope.
- the electrode material is not particularly limited, but it is preferable to use a material capable of concentrating the electric field as much as possible, such as a copper mesh, in order to stabilize discharge. This is to avoid abnormal discharge from a specific weak point on the electrode surface, and is important to maintain a stable glow discharge at a pressure near atmospheric pressure.
- the poly and oligosilane compounds synthesized in the present invention are stored in a refrigerated dark place after filling with an inert gas, but all subsequent operations must be performed in an inert gas atmosphere.
- the removal of impurity ions contained in the material is not particularly limited, but distillation, ion exchange, and the like are generally used.
- the poly and oligosilane compounds thus obtained can be used in a state dissolved in neat or solvent.
- the solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as cyclooctane and cyclohexanone, aromatic solvents such as benzene, tetrahydrofuran, dimethyl sulfoxide and the like.
- the concentration of the silane compound in the solvent is, for example, 0.1 to 30% by mass, or 1 to 20% by mass.
- dissolved oxygen and water in the solvent which must be removed sufficiently. Although it is preferable that dissolved oxygen and water are substantially zero, it can be carried out in a solvent that is usually present in a trace amount.
- the removal of dissolved oxygen is not particularly limited, and argon, nitrogen gas bubbling, vacuum degassing, or the like can be used.
- a poly or oligosilane solvent prepared using a solvent from which moisture and dissolved oxygen have been removed is not particularly limited, but in general, spin coating, dipping, ink jet, dropping, screen printing, bar coating, etc.
- a thin film can be formed on the substrate.
- polysilane or oligosilane thinned on a substrate is usually baked on a hot plate and stabilized as an amorphous film.
- the temperature required at this time is said to be about 300 ° C.
- the obtained amorphous film is usually a silicon film when no impurities are present in polysilane or oligosilane, and does not exhibit p-type or n-type semiconductor characteristics.
- a trivalent or pentavalent element is bonded to silicon with respect to this amorphous silicon film, thereby generating a bonding defect and making a carrier. This operation is referred to as doping.
- doping When doping is performed on a film that has been made amorphous in this way, it is necessary to implant ions with large energy. These operations are generally performed under vacuum or ultra vacuum.
- a method in which a silane compound is converted into amorphous silicon by first preliminarily heating a substrate coated with oligo or polysilane or directly irradiating plasma. It is a very useful technique for plasticizing devices made of silicon because it does not require particularly high heat. That is, the Si—H bond of oligosilane is cleaved by the thermoelectrons of the above-mentioned thermal non-equilibrium atmospheric pressure plasma, ions or radical species contained in the plasma, and Si—Si bonds are formed.
- the dielectric barrier type plasma has a lower plasma density, so the gas temperature is about room temperature. However, since the electron temperature reaches several tens of thousands to several million kelvin, it can be used for such a reaction.
- the method of forming amorphous silicon using oligo or polysilane is not particularly limited.
- it can be formed by directly irradiating plasma to an oligo or polysilane coat film, but heating (for example, 50 ° C. to 300 ° C.)
- It can also be formed by irradiating the plasma after the solvent is removed by a treatment such as the above.
- plasma irradiation is performed with the solvent remaining, a Si—C bond in which a decomposition component of the solvent and silicon are bonded is formed. For this reason, when a silicon carbide film is required, it is necessary to irradiate the plasma on the surface where the solvent remains.
- the solvent remaining in the coat film must be removed in advance.
- a low boiling point solvent it is carried out by heating with a hot plate or the like.
- An amorphous silicon film can be formed by irradiating the oligo or polysilane film from which the residual solvent has been removed with plasma. At this time, the heat applied to the thin film is sufficient at a temperature necessary for the solvent to volatilize.
- the method for doping impurities into the amorphous silicon film thus formed is not particularly limited.
- a boron compound such as decaborane is dissolved in the oligo or polysilane solvent, By irradiating plasma directly or after removing the solvent on the thin film coated on the substrate, the BH bond and the Si-H bond are cut by the plasma particles or ions and radicals contained therein, together with the Si-Si bond. Si—B bonds are formed. Thereby, boron doping to the amorphous silicon film is performed.
- phosphorous compounds such as red phosphorus and yellow phosphorus as dope of pentavalent element are dissolved in the oligo or polysilane solvent like decaborane, and applied to the substrate and thinned to irradiate plasma directly or after removing the solvent. Then, the P—H bond and the Si—H bond are cleaved by the plasma particles or ions and radicals contained therein, and a Si—P bond is formed together with the Si—Si bond.
- the doped amorphous silicon thus obtained has been confirmed to function as an n-type and p-type semiconductor, respectively.
- These Si—B and Si—P bond formation can be easily analyzed by X-ray photoelectron spectroscopy, and by using this method, it is confirmed that Si—B and Si—P bonds are formed by these methods. confirmed.
- Regarding the operability of these oligosilanes it is said that the Si—Si bond is cleaved by ultraviolet irradiation to form a cyclic compound, and the produced cyclic silane has an effect of easily forming a Si—Si bond.
- the plasma used in the present invention generates ultraviolet rays of various wavelengths from radicals derived from nitrogen gas and further ions under a nitrogen atmosphere (Fig. 3). We found that what we were doing could be done simultaneously by plasma irradiation alone.
- a semiconductor film can be formed by a low temperature treatment without requiring a high temperature as in the prior art, and is a very useful technique for plasticizing semiconductor devices. is there.
- Synthesis Example 1 Synthesis of Catalytic Diphenyldicyclopentadienyl Zirconium Cp 2 ZrPh 2
- dichlorodicyclopentadienyl zirconium Cp 2 ZrCl 2 5.0 g
- DME 1, 2-dimethoxyethane
- the filtrate was concentrated under reduced pressure at 20 ° C./10 Torr, and the solid content obtained was washed with 60 mL of diethyl ether (Et 2 O) and then dried under reduced pressure at 20 ° C./5 Torr to obtain the target catalyst diphenyldicyclopentadienylzirconium Cp. 2 ZrPh 2 (5.53 g) was obtained.
- Synthesis Example 2 Synthesis of Polyphenylsilane Under a nitrogen atmosphere, diphenyldicyclopentadienylzirconium Cp 2 ZrPh 2 (0.165 g) synthesized in Synthesis Example 1 was charged as a catalyst in a 100 mL reaction flask, and 24 to 26 was added thereto. Phenylsilane PhSiH 3 (10 g) was added at 0 ° C., and the mixture was stirred at the same temperature for 89 hours.
- the chain polyphenylsilane had a number average molecular weight of 1481, a weight average molecular weight of 1771 and a polymerization degree of 14.
- the cyclic polyphenylsilane had a number average molecular weight 631, a weight average molecular weight 644, and a degree of polymerization of 5 to 6.
- Example 1 Nitrogen doping into oligosilane: 10 ⁇ L of the cyclopentadiene solution (10 mass%) of polyhydrosilane obtained in Synthesis Example 3 was applied on a silicon wafer, and a thin film was obtained by spin coating (1500 rpm, 10 seconds). The obtained thin film was irradiated with plasma immediately after spin coating to perform nitrogen doping. After completion of the doping, the substrate was not subjected to main firing, and was evaluated as a target nitrogen-doped amorphous silicon film.
- Plasma irradiation conditions were as follows: Helium gas with a purity of 99.99% was passed through a glass discharge tube having an inner diameter of 2 mm and an outer diameter of 3 mm in a glove box filled with nitrogen gas at a rate of 60 liters / minute, and a frequency of 10 kHz and a voltage of 10 kV were applied. Applied. Examination of plasma irradiation conditions for the purpose of doping nitrogen into the polyhydrosilane obtained in Synthesis Example 3: The substrate coated under the above conditions was baked under the following conditions, and then plasma was irradiated for 5 minutes to perform nitrogen doping. No main firing was performed after the dope. Table 2 shows the nitrogen doping conditions for the thin film using the polyhydrosilane obtained in Synthesis Example 3.
- the surface of the substrate doped with nitrogen by each processing method was analyzed by XPS, and the bonding state in the vicinity of the surface was analyzed.
- the analysis results of nitrogen, oxygen, carbon, and silicon near the surface are shown in FIG.
- the amount of nitrogen present on the surface depends on the firing temperature and the plasma irradiation conditions. In particular, nitrogen was detected at a very high rate from the plasma irradiated after 200 ° C. for 5 seconds. I understand that.
- Example 2 Examination of plasma irradiation conditions for the purpose of doping boron atoms into the polyhydrosilane obtained in Synthesis Example 3: Using decaborane as a boron source, 0.1 g of polyhydrosilane obtained in Synthesis Example 3 was dissolved in 0.9 g of a cyclooctane solution (10 mass%) of decaborane (when decaborane was dissolved in a 10 mass% solution of polyhydrosilane). Care must be taken because it is difficult to dissolve). A decaborane-dissolved polyhydrosilane solution dissolved by stirring in a glove box was applied onto a silicon wafer under the following conditions.
- Condition 1 Immediately after application of the polyhydrosilane (containing decaborane) obtained in Synthesis Example 3, plasma irradiation (3 minutes), heating at 100 ° C. for 10 minutes, and heating at 300 ° C. for 1 hour were performed.
- Condition 2 After the polyhydrosilane (containing decaborane) obtained in Synthesis Example 3 was applied, baking was performed at 130 ° C. for 10 minutes, and after 3 minutes of plasma irradiation, heating was performed at 300 ° C. for 1 hour.
- Condition 3 After applying polyhydrosilane (containing double amount of decaborane) obtained in Synthesis Example 3, after baking at 130 ° C. for 10 minutes, heating was performed at 300 ° C. for 1 hour.
- Plasma irradiation conditions were as follows: a glass discharge tube having an inner diameter of 2 mm and an outer diameter of 3 mm was flowed with helium gas having a purity of 99.99% at 60 liters / min to fill the glove box with helium, and a frequency of 10 kHz and a voltage of 10 kV were applied. did.
- the said decaborane containing polyhydrosilane solution was apply
- Example 4 Cyclopentasilane was synthesized by the method shown in [Chemical Formula 5]. That is, cyclic- (SiPhPh) 5 was produced using Ph 2 SiCl 2 in tetrahydrofuran and using Li metal as a catalyst. However, Ph shows a phenyl group. This cyclic- (SiPhPh) 5 was blown with HCl gas at room temperature in the presence of AlCl 3 in cyclohexane to produce cyclic- (SiClCl) 5 , and this was reacted with LiAlH 4 in diethyl ether at 0 to 10 ° C. -(SiHH) 5 was produced.
- This cyclopentasilane was polymerized to obtain a polymer of cyclopentasilane.
- a solution in which 0.05 g of decaborane was dissolved in cyclooctane was prepared and added to 1 mL of a polymer of cyclopentasilane to dissolve.
- the obtained solution was applied onto a quartz substrate, and plasma was continuously irradiated while the sample was heated at 100 ° C. until the solvent was volatilized.
- Plasma irradiation conditions were as follows: a glass discharge tube having an inner diameter of 2 mm and an outer diameter of 3 mm was flowed with helium gas having a purity of 99.99% at 60 liters / min to fill the glove box with helium, and a frequency of 10 kHz and a voltage of 10 kV were applied. did. After the plasma irradiation, the silicon film obtained by baking at 300 ° C. for 1 hour and then at 450 ° C. for 1 hour was collected, and radicals in the film were measured by ESR. The results are shown in FIG.
- Example 5 The same polymer of cyclopentasilane as in Example 4 was used. Each solution in which 0.01 g, 0.025 g, and 0.05 g of decaborane was dissolved in cyclooctane was prepared, and each was added to 1 mL of a polymer of cyclopentasilane and dissolved. Each of the obtained solutions was applied onto a quartz substrate, and the sample was continuously irradiated with plasma at room temperature until the solvent was volatilized.
- Plasma irradiation conditions were as follows: a glass discharge tube having an inner diameter of 2 mm and an outer diameter of 3 mm was flowed with helium gas having a purity of 99.99% at 60 liters / min to fill the glove box with helium, and a frequency of 10 kHz and a voltage of 10 kV were applied. did.
- helium gas having a purity of 99.99% at 60 liters / min to fill the glove box with helium, and a frequency of 10 kHz and a voltage of 10 kV were applied. did.
- Each silicon film obtained by baking at 150 ° C. for 1 hour after plasma irradiation was collected, and radicals in the film were measured by ESR.
- the case where 0.01 g of decaborane was added to 1 mL of the polymer of cyclopentasilane is shown in FIG.
- FIG. 11 shows a case where 0.05 g of decaborane was added to 1 mL of the silane polymer.
- Example 6 The same polymer of cyclopentasilane as in Example 4 was used. 0.5 mL of a phosphorus doping solution ACCUSPIN P8545 manufactured by Honeywell was added to 1 mL of a polymer of cyclopentasilane and dissolved. The obtained solution was applied on a quartz substrate, and the sample was continuously irradiated with plasma at room temperature until the solvent was volatilized.
- Plasma irradiation conditions were as follows: a glass discharge tube having an inner diameter of 2 mm and an outer diameter of 3 mm was flowed with helium gas having a purity of 99.99% at 60 liters / min to fill the glove box with helium, and a frequency of 10 kHz and a voltage of 10 kV were applied. did. After the plasma irradiation, baking was performed at 300 ° C. for 1 hour, and the obtained silicon film was scraped off and collected in the form of particles, and radicals in the film were measured by ESR. The results are shown in FIG.
- the measurement of the ESR is as follows: magnetic field: 337.5 ⁇ 7.5 mT, modulation magnetic field: 0.3 mT, time constant: 0.03 seconds, microwave output: 1 mW, microwave frequency: near 9.445 GHz The time was 2 minutes.
- the present invention relates to a technique for producing a coating type amorphous silicon semiconductor film, and is a technique useful for forming an inorganic semiconductor film by an unprecedented low-temperature operation.
- This technology can be a great advantage especially for the plasticization of semiconductor devices, and can be widely applied to lighter electronic devices in the future.
- Gas flow pipe 1a.
- Gas outlet Electrodes 3.
- Plasma generation electrode 4.
- voltage application device Non-equilibrium plasma jet, 6. 6. high frequency power supply;
- Mesh electrode Plasma gas, 10.
- ESR spectrum measurement curve showing holes formed in boron-derived valence band formed by plasma irradiation;
- ESR spectrum measurement curve showing electrons formed in the vicinity of a phosphorus-derived conductor formed by plasma irradiation.
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Abstract
Description
マイナス極からプラス極への電子流を微少物質を介して形成し、電位差に基づいて微少物質の表面にプラズマを誘起してプラズマ反応により生成した反応物質の生成を行う方法(特許文献1参照)がある。
反応炉内に薄膜の材料となる反応ガスを導入し、電極間に電圧を印加してプラズマを生成し反応ガスを分解すると共に化学反応を起こさせて基板上に薄膜を堆積させる薄膜形成方法(特許文献2参照)がある。
プラズマCVD法は、シランガス(SiH4)などSi系材料ガスに電気的エネルギーを印加してプラズマ生成させ、活性なラジカルやイオンを生成させ、活性環境下で化学反応を行わせるものである。
この生成するプラズマは電子温度とガス温度の2つの温度を持ち、これら両者が共に数万ケルビンと高い高温プラズマと、電子温度は数万ケルビンと高いがガス温度は室温から数百℃と低い低温プラズマとがあり、特にこの低温プラズマを用いると基板温度を低温に保ったままで薄膜形成が行えることから、従来用いられてきた熱CVD法のように基板を1000℃近い温度まで上げなくてはならないのに対して、基板を低温に保った状態で薄膜形成を行える利点がある。
これら薄膜に対するドーピングは一般には気相ドーピング法が一般的に行われる。SiH4ソースに対してPH3、AsH3(n型)、B2H6(p型)などの不純物ガスを加えながら反応させることで簡単にドーピングすることができる。
以上プラズマCVD法や光CVD法ではアモルファスシリコン膜を比較的低温(300℃程度)で得ることができると同時にSiH4と他の混合ガスを用いることで固相表面若しくは気相中でこれら2種以上の分子を反応させ異種元素間結合を作り上げることが可能である。
また、膜形成中に形成されるダングリングボンドは結晶成長中に何らかの不純物元素と結合して、単結晶シリコン中では禁止帯に相当するエネルギーを持つ電子状態を形成する。これは、少数キャリアに対してトラップサイトや再結合中心として働き、一般的にはデバイス寿命を短くする。プラズマCVD法などではこれらダングリングボンドに対して水素を用いた短絡を行い不活性化しなくてはならない。この操作もCVD装置の中で行う必要があり、ここでも超真空チャンバーが必要となるなどプロセス的にも問題がある。
また、これらシリコン膜に対するドーピングは単結晶シリコン製造工程と同様に行われるが、これに対して気相法で多結晶シリコンを製造する場合は先に述べたCVDによるアモルファスシリコンの成膜後に更に溶融加熱して単結晶化する方法が取られ、最終的には液相法と同程度の加熱処理が必要となることが問題であった。
第2観点として、上記異種元素結合を含む化合物が、周期律表の第13族乃至第15族に含まれる元素同士の異種元素間結合を含む化合物である第1観点に記載の製造方法、
第3観点として、上記プラズマ又はプラズマにより励起された周囲のガスのラジカルを上記被照射体に照射すると共に、更に上記被照射体に紫外線を照射することを特徴とする第1観点又は第2観点に記載の製造方法、
第4観点として、上記異種元素結合を含む化合物が、基板上に被膜として得られる請求項1乃至請求項3のいずれか1項に記載の製造方法第1観点乃至第3観点のいずれか一つに記載の製造方法、
第5観点として、上記被照射体は、上記元素単体、上記化合物、上記元素単体を含む溶液、上記化合物を含む溶液、上記元素単体のガス及び上記化合物のガスからなる群から選択される2種以上である第1観点乃至第4観点のいずれか一つに記載の製造方法、
第6観点として、上記被照射体は、その1種が第14族元素を含む化合物であり、他の1種が第4族乃至第15族に含まれる元素単体のガス又は該元素を含む化合物のガスである第1観点乃至第5観点のいずれか一つに記載の製造方法、
第7観点として、上記被照射体は、その1種が第14族元素を含む化合物であり、他の1種が第13族元素の単体若しくはその元素を含む化合物又は第15族元素の単体若しくはその元素を含む化合物であり、第14族元素を含む化合物1モルに対して第13族元素の単体若しくはその元素を含む化合物又は第15族元素の単体若しくはその元素を含む化合物を0.2乃至10モルの割合で含むものである、第1観点乃至第6観点のいずれか一つに記載の製造方法、
第8観点として、上記異種元素間結合を含む化合物が、Si-Si結合と、Si-B結合又はSi-P結合とを含むものである第1観点に記載の製造方法、
第9観点として、第14族元素を含む化合物が式(1):
第10観点として、上記第13族元素の単体又はその元素を含む化合物が式(5):
第11観点として、上記第15族元素の単体又はその元素を含む化合物が式(6):
第12観点として、上記放電管の内部又は上記平板電極の間に導入するガスが、ヘリウム、ネオン、アルゴン、クリプトン、キセノン、窒素分子、酸素分子、水素分子、二酸化炭素、一酸化窒素、二酸化窒素、アンモニア、ハロゲン分子、ハロゲン化水素、二硫化硫黄、硫化水素、及び水蒸気からなる群から選ばれる少なくとも1種のガスである第1観点乃至第11観点のいずれか一つに記載の製造方法、
第13観点として、上記放電管の内部又は上記平板電極の間に導入するガスが、ヘリウム単独ガス、又はヘリウムと水素分子、酸素分子、窒素分子、二酸化炭素、一酸化炭素、フッ素分子、及び塩素分子からなる群より選ばれる少なくとも1種のガスとの混合ガスである第1観点乃至第11観点のいずれか一つに記載の製造方法、
第14観点として、上記2枚の金属又は絶縁体の平板電極は対面し、その一方に高電圧電極を接続し、その他方はアースを接続せず大気アースとするか又はアース電極を接続した構造であり、両電極間にガスを流して電極間に存在する分子をプラズマ化することを特徴とする第1観点乃至第13観点のいずれか一つに記載の製造方法、
第15観点として、上記2枚の金属又は絶縁体の平板電極は減圧容器中にあり、減圧後に導入ガスを流し、低いガス圧下で低周波数で高電圧を印加して電極間に存在する分子をプラズマ化することを特徴とする第1観点乃至第14観点のいずれか一つに記載の製造方法、
第16観点として、上記金属管の放電管又は金属の平板電極が第4族乃至第14族に含まれる元素単体又はそれを含む混合物からなる第1観点乃至第15観点のいずれか一つに記載の製造方法、
第17観点として、上記絶縁体管の放電管又は絶縁体の平板電極が合成高分子、天然高分子、ガラス、又はセラミックスからなる第1観点乃至第15観点のいずれか一つに記載の製造方法、及び
第18観点として、プラズマ発生に用いられる電源が10Hz乃至100MHzの周波数、1000V乃至30000Vの出力電圧である、低温でプラズマ照射することを特徴とする第1観点乃至第17観点のいずれか一つに記載の製造方法である。
本発明は低温の大気圧プラズマジェットを用いた異種金属結合形成技術に関すものであり、特に塗布法で成膜可能なオリゴシラン化合物を用いたシリコン膜への第13族元素又は第15族元素のドーピングに対して有用な技術である。
即ち、プラズマジェットという高いエネルギーを有する電離気体の状態をガス圧力と電界で制御することにより、プラズマによる化学反応をコントロールし、シリコン薄膜への異種元素のドーピングを大気圧付近で更に低温で行うことが可能なものである。
異種元素結合を含む化合物は周期律表の第4族元素乃至第15族元素間の異種元素結合を含むが、更には周期律表の第13族元素乃至第15族元素間の異種元素結合を含むものである。異種元素結合を含むとは、同種元素結合と異種元素結合からなることを意味する。異種元素結合を含む化合物は第13族元素をドープした第14族元素としては、(第13族元素)/(第14族元素)が1×10-1乃至1×10-6の範囲であり全水素量は15原子%乃至25原子%程度であり、第15族元素をドープした第14族元素としては、(第15族元素)/(第14族元素)が1×10-2乃至1×10-5の範囲であり全水素量はほぼ15原子%である。
大気圧下とはプラズマが噴出する環境の圧力を示し、特に限定するものではないが例えば溶液の蒸気圧以上、10気圧以下の範囲、更に好ましくは大気解放下で反応を行う大気圧は減圧、加圧装置を必要とせず好適である。
上記異種元素結合を含む化合物が、基板上に2種以上の、元素単体又はその化合物を被照射体として被覆して、これにプラズマを照射することにより基板上に被膜として得ることができる。
上記被照射体は、その1つとして第14族元素を含む化合物を用い、もう1つとしてガスを用いることができる。
また上記被照射体は、その1つとして第14族元素の単体又はその元素を含む化合物を用い、他の1つとして第13族元素、第15族元素の単体又はそれらの元素を含む化合物を用いることができる。第13族元素、第15族元素の単体又はそれらの元素を含む化合物はガスとして用いることができる。
式(1)は鎖状シラン化合物(直鎖及び分岐状シラン化合物を含む。)であり、nは2乃至40、又は2乃至30の整数である。式(2)及び式(3)は環状シラン化合物であり、hは3乃至10の整数である。式(4)は籠状シラン化合物であり、mは6、8又は10である。
式(5)においてiは1乃至10の整数であり、jは0乃至12の整数で示されるホウ素成分が挙げられる。jがゼロの時はホウ素単体である。またjが1乃至12の時は水素化ホウ素(ボラン)である。モノボラン(BH3)、ジボラン(B2H6)、テトラボラン(B4H10)、デカボラン(B10H14)等が挙げられる。
また第13族元素の単体又はその元素を含む化合物としてはガリウム、インジウム、又はそれらの化合物を用いることができる。
式(6)においてwは1乃至10の整数であり、uは0乃至12の整数で示されるリン単体又は含リン化合物が挙げられる。uがゼロの時はリン単体である。またuが1乃至12の時は水素化リンである。リン単体としては白リン、赤リン、黄リン、黒リン、化合物としてはホスフィン(PH3)等が挙げられる。
また、第15族元素の単体又はその化合物としては窒素ガス、含窒素化合物、ヒ素、含ヒ素化合物を用いることができる。含窒素化合物としてはアミン、硝酸、ジアゾ化合物等が挙げられる。含ヒ素化合物としては水素化ヒ素が挙げられる。
第14族元素を含む化合物1モルに対して第13族元素の単体若しくはその化合物又は第15族元素の単体若しくはその化合物を0.2乃至10モル、好ましくは1乃至5モルの割合で用いることができる。
電極に金属管を用いる場合には高電圧電極のみを金属管に接続し、グラウンドは大気とする(図2b)。また、プラスチック管を用いる場合には、高電圧電極の前後(接触しない、またアーク放電しない距離以上はなす。)にアースを取り付けることもできるが、金属管同様に大気をグランドにすることもできる。プラズマの発生に必要な電源として交流の高電圧電源を用いる。交流とは10Hz乃至100MHzを示し、好ましくは50Hz乃至100kHz、更に好ましくは5kHz乃至20kHzである。交流電圧は1000V乃至30000Vの範囲でプラズマ発生が可能であるが、好ましくは1000V乃至20000V、更に好ましくは5000V乃至8000Vである。
電極材料としては特に限定するものではないが、例えば金属としてアルミニウム(管)、ステンレス(管)、銅(管)、鉄(管)、真鋳(管)など、ガス流路の形成されている金属管の放電管又は金属の電極は何れも使用が可能である。
また、上記プラスチックのほかに無機セラミック材料を絶縁体管又は絶縁電極として用いることもできる。これら具体例としては、特に限定するものではないが、ガラス、シリコン、ジルコニア、陶磁器、アルミナ、チタニア、シリコンカーバイト、シリコンナイトライドなどが挙げられる。
ヘリウムガスは大気中で安定したプラズマを作りやすく一般的によく用いられる。用いられるガスの流量はプラズマパラメーターに影響するファクターであるが、一般にその流量は1ミリリットル/秒以上であり、1000ミリリットル/秒以下の範囲で使用可能である。好ましくは10ミリリットル/秒以上で500ミリリットル/秒以下、更に好ましくは30ミリリットル/秒以上で100ミリリットル/秒以下で使用することができる。
これに対して混合ガスではなく上記シラン化合物溶液に常温固体、例えばデカボランを溶解し、この溶液をもと作成した薄膜に対して上記熱非平衡プラズマを照射することにより室温付近の温度でSi-Si結合中にSi-B結合を形成することができる。このほかドーパントとして使用可能な化合物としては、特に限定するものではないが、黄燐、赤燐なども可能である。
そして、2枚の金属又は絶縁体の平板電極が減圧容器中にあり、減圧後に導入ガスを流し、低ガス圧下で低周波数で高電圧を印加して導入ガスをプラズマ化させて用いることができる。
平行平板電極を用いた場合その電極材料としては特に限定するものではないが、放電を安定させるため例えば銅のメッシュなどできるだけ電界集中できる材料を用いることが好ましい。これは、電極表面にある特定の弱点からの異常放電をさけるためであり、大気圧近傍の圧力において安定なグロー状放電を維持するために重要である。
このようにして得られたポリ及びオリゴシラン化合物はニート若しくは溶剤に溶解した状態で用いることができる。溶剤は特に限定するものではないが、例えばシクロオクタン、シクロヘキサノンなど炭化水素系溶剤やベンゼン等芳香族系溶剤、更にテトラヒドロフラン、ジメチルスルフォキシドなどが挙げられる。溶剤中でのシラン化合物の濃度は例えば0.1乃至30質量%、又は1乃至20質量%で得られる。
溶存酸素の除去は特に限定するものではないが、アルゴン、窒素ガスのバブリングや減圧脱気などを用いることができる。
水分及び溶存酸素を除去した溶剤を用いて作成したポリ若しくはオリゴシラン溶剤は特に限定するものではないが一般にはスピンコート法、ディップ法、インクジェット法、滴下法、スクリーン印刷法、バーコート法などによって目的とする基板上に薄膜形成することができる。
即ち、上記の熱非平衡大気圧プラズマの熱電子やプラズマ中に含まれるイオンやラジカル種によりオリゴシランのSi-H結合が切断されSi-Si結合を形成するものである。特に誘電体バリア型プラズマでは更にプラズマ密度が低くなることからそのガス温度はほぼ室温である。しかし、電子温度は数万ケルビンから数百万ケルビンにも達するためこのような反応に使用できるのである。
特に溶剤が残留したままプラズマの照射を行うと、溶剤の分解成分と珪素とが結合したSi-Cの結合が形成される。このため、シリコンカーバイト膜が必要とされる場合はむしろ溶剤残存した表面に対して当該プラズマを照射することが必要となる。一方、膜中にSi-C結合があってはならない場合は、コート膜中に残存する溶剤は予め除去する必要がある。通常、低沸点溶剤の場合はホットプレート等による加熱で行われる。残存溶剤を除去したオリゴ若しくはポリシラン膜に対してプラズマを照射することによりアモルファスシリコン膜を形成することができる。このとき薄膜に対してかかる熱は溶剤が揮発するのに必要な温度で十分である。
これら、Si-BおよびSi-P結合形成はX線光電子分光法によって容易に分析可能であり、この手法をもちいることによりこれら手法でSi-BおよびSi-P結合が形成されていることが確認された。
これらオリゴシランの操作性に関しては、紫外線照射によりSi-Si結合が切断され環状化合物となり、生成した環状シランがSi-Si結合を形成しやすくなる効果があるといわれている。本発明で用いられるプラズマは窒素雰囲気下において窒素ガス由来のラジカル、更にはイオンから様々な波長の紫外線が発生しており(図3)、このことから従来、紫外線照射とアモルファス化をバッチ式で行っていたものを、プラズマ照射のみで同時に行えることがわかった。
本発明のアモルファスシリコン半導体薄膜の合成及び表面処理に関して、従来のような高温を必要とせず、低温での処理により半導体膜を形成できるものであり、半導体デバイスのプラスチック化に非常に有用な技術である。
〔合成例1〕触媒ジフェニルジシクロペンタジエニルジルコニウムCp2ZrPh2の合成
窒素雰囲気下、300mLの反応フラスコにジクロロジシクロペンタジエニルジルコニウムCp2ZrCl2(5.0g)と溶剤としてDME(1,2-ジメトキシエタン)39mLを仕込み、0乃至10℃とした。これに同温にて濃度37.1mol/Lのフェニルマグネシウムブロミド(PhMgBr)のTHF(テトラヒドロフラン)溶液34.37mLを滴下し、その後24乃至26℃にて19時間、撹拌した。20℃/20Torrで減圧濃縮後、ジエチルエーテル(Et2O)8mLを加えて24乃至26℃にて1時間撹拌した。さらにトルエン39mLを加えて同温にて30分間撹拌後、反応溶液をろ過した。ろ液を20℃/10Torrで減圧濃縮して得られた固形分をジエチルエーテル(Et2O)60mLで洗浄後、20℃/5Torrで減圧乾燥して目的の触媒ジフェニルジシクロペンタジエニルジルコニウムCp2ZrPh2(5.53g)を得た。
窒素雰囲気下、100mL反応フラスコに触媒として合成例1で合成したジフェニルジシクロペンタジエニルジルコニウムCp2ZrPh2(0.165g)を仕込み、これに24乃至26℃にてフェニルシランPhSiH3(10g)を加え、同温にて89時間撹拌した。これにトルエン(47g)を加えた後、3%HCl(68g×5回)を加えて撹拌洗浄、分液後、イオン交換水(68g)を加えて撹拌洗浄した。有機層をトルエン(118g)を溶離液としてフロリジール(27g)カラムクロマトグラフィーで精製、濃縮後、80℃で2時間乾燥して目的のポリフェニルシラン(8.87g)を得た。得られたポリフェニルシランは式(1)に相当する鎖状ポリフェニルシランと式(2)に相当する環状ポリフェニルシランの割合がモル比で59対41であった。鎖状ポリフェニルシランは数平均分子量1481、重量平均分子量1771、重合度14であった。環状ポリフェニルシランは数平均分子量631、重量平均分子量644、重合度5乃至6であった。
褐色の100mL反応フラスコに合成例2で合成したポリフェニルシラン(5.0g)と溶剤としてシクロヘキサン(43.5g)を仕込んだ。これに塩化アルミニウムAlCl3(0.41g)を加えた後、液体窒素で凝固させた。これを水浴で室温まで昇温させ、窒素置換した。これに塩酸HClガスを流速(950mL/分)で10時間吹込んだ。その後、減圧と窒素による復圧を10回繰返して脱塩酸HClした。これに窒素雰囲気下、0乃至10℃にて水素化アルミニウムリチウムLiAlH4(1.17g)を含むジエチルエーテル(Et2O)13.72gの溶液を30分かけて滴下した。室温で12時間撹拌後、反応溶液をイオン交換水(11g)中へ注ぎ込み、1分間撹拌、静置後、上澄み液をデカンテーションした。この水洗操作を3回繰り返した後、有機層をメンブレンフィルターでろ過、濃縮、減圧乾燥して目的のポリハイドロシラン(0.94g)を得た。
オリゴシランへの窒素ドープ:
合成例3で得られたポリハイドロシランのシクロペンタジエン溶液(10質量%)をシリコンウエハー上に10μL塗布し、スピンコート(1500rpm、10秒)により薄膜を得た。得られた薄膜に対して、スピンコート後直ちにプラズマ照射を行い、窒素ドープを行った。ドープ終了後基板は本焼成せず、目的とする窒素ドープアモルファスシリコン膜として評価を行った。プラズマ照射の条件は窒素ガスを充填したグローブボックス内で内径2mm、外径3mmのガラス製放電管に純度99.99%のヘリウムガスを60リットル/分で流し、10kHzの周波数、10kVの電圧を印加した。
合成例3で得られたポリハイドロシランへの窒素ドープを目的とするプラズマ照射条件の検討:
上記条件で塗布した基板を以下の条件で焼成し、その後プラズマを5分照射し窒素ドープを行った。ドープ後本焼成は行わなかった。合成例3で得られたポリハイドロシランを用いた薄膜への窒素ドープ処理条件を表2に示した。
図5からわかるように表面に存在する窒素の量は焼成温度及びプラズマ照射条件に依存しており、特に200℃5秒加熱処理した後にプラズマ照射したものから非常に高い割合で窒素が検出されていることがわかる。
合成例3で得られたポリハイドロシランへのホウ素原子ドープを目的とするプラズマ照射条件の検討:
デカボランをホウ素源として用い、デカボランのシクロオクタン溶液(10質量%)0.9gに合成例3で得られたポリハイドロシラン0.1gを溶解した(ポリハイドロシラン10質量%溶液にデカボランを溶解すると溶解しにくいので注意が必要)。グローブボックス中で撹拌溶解したデカボラン溶解ポリハイドロシラン溶液を次の条件でシリコンウエハー上に塗布した。
条件1:合成例3で得られたポリハイドロシラン(デカボラン含有)塗布後直ちにプラズマ照射(3分間)後、100℃10分間加熱後、300℃1時間加熱を行った。
条件2:合成例3で得られたポリハイドロシラン(デカボラン含有)塗布後130℃10分間焼成、その後プラズマ照射3分間後、300℃で1時間加熱を行った。
条件3:合成例3で得られたポリハイドロシラン(デカボラン倍量含有)塗布後130℃10分間焼成後、300℃1時間加熱を行った。
条件4:合成例3で得られたポリハイドロシラン(デカボラン倍量含有)塗布後130℃5分間焼成後、プラズマ照射3分間後、300℃1時間加熱を行った。
プラズマ照射の条件は内径2mm、外径3mmのガラス製放電管に純度99.99%のヘリウムガスを60リットル/分で流しグローブボックス内にヘリウムを充満し、10kHzの周波数、10kVの電圧を印加した。
上記デカボラン含有ポリハイドロシラン溶液をシリコン基板上に塗布し、各種条件で作成した基板をXPSにより分析し、含有元素の状態を観察した。分析元素は炭素、窒素、酸素、珪素、ホウ素でそれぞれ3点測定を行った。結果を図6に示す。
ホウ素ドープ膜の電気特性評価:
白金電極くし型電極(L/S=10/10、石英基板)に合成例3で得られたポリハイドロシランをスピンコートし、得られた薄膜を上記条件1、2、4でそれぞれ処理した。これら得られた基板の電圧電流特性の評価を行った。測定は全て室温で行った。結果を図7に示す。図7中の符号10は上記条件2で得られた膜の電圧電流特性を示し、符号11は上記条件1で得られた膜の電圧電流特性を示した。
図7から明らかなようにプラズマ焼成前の仮焼成有り無しで比較すると、仮焼成を行いプラズマ照射を行った場合、低電圧側において仮焼成しないでプラズマ照射を行ったものより大きな電流が流れている。しかし、高電圧になるに従い仮焼成しプラズマ照射した膜に対して、仮焼成なしでプラズマ照射したものの方が大きな電流が流れることがわかる。電圧電流カーブを解析すると低電圧側ではオーミック性電流が流れていることから、内部キャリアがその電流を支配していると予想される。即ち、ホウ素ドープによる効果が出たものと予想され、さらにバルク結晶中のキャリア濃度は恐らく条件1の方が多いことになる。しかし、高電圧側では、電圧の2乗で電流値が増大しており、電流が空間電荷で支配されていることが予想される。いずれにしてもホウ素ドープにより大きな電流が流れることが確認できた。
〔化5〕で示された方法でシクロペンタシランを合成した。即ち、Ph2SiCl2をテトラヒドロフラン中でLi金属を触媒として環状-(SiPhPh)5を製造した。但しPhはフェニル基を示す。この環状-(SiPhPh)5をシクロヘキサン中でAlCl3の存在下に室温でHClガスを吹き込み環状-(SiClCl)5を製造し、これに0乃至10℃でジエチルエーテル中でLiAlH4を反応させ環状-(SiHH)5を製造した。このシクロペンタシランは、重合し、シクロペンタシランの重合物を得た。
0.05gのデカボランをシクロオクタンに溶解した溶液を作成し、シクロペンタシランの重合物1mLに添加して溶解した。
得られた溶液を石英基板上に塗布し、サンプルを100℃で加熱しながらプラズマを溶媒が揮発するまで継続して照射した。プラズマ照射の条件は内径2mm、外径3mmのガラス製放電管に純度99.99%のヘリウムガスを60リットル/分で流しグローブボックス内にヘリウムを充満し、10kHzの周波数、10kVの電圧を印加した。
プラズマ照射後300℃1時間、その後450℃1時間の焼成を行い得られたシリコン膜を回収し、ESRにより膜中のラジカルを測定した。結果を図8に示す。
実施例4と同じシクロペンタシランの重合物を用いた。0.01g、0.025g、及び0.05gのデカボランをシクロオクタンに溶解したそれぞれの溶液を作成し、それぞれシクロペンタシランの重合物1mLに添加して溶解した。
得られた溶液をそれぞれ石英基板上に塗布し、サンプルを室温でプラズマを溶媒が揮発するまで継続して照射した。プラズマ照射の条件は内径2mm、外径3mmのガラス製放電管に純度99.99%のヘリウムガスを60リットル/分で流しグローブボックス内にヘリウムを充満し、10kHzの周波数、10kVの電圧を印加した。それぞれプラズマ照射後150℃1時間の焼成を行い得られたシリコン膜を回収し、ESRにより膜中のラジカルを測定した。シクロペンタシランの重合物1mLに0.01gのデカボランを添加したケースを図9で示し、またシクロペンタシランの重合物1mLに0.025gのデカボランを添加したケースを図10で示し、そしてシクロペンタシランの重合物1mLに0.05gのデカボランを添加したケースを図11で示した。
実施例4と同じシクロペンタシランの重合物を用いた。シクロペンタシランの重合物1mLにハネウェル社製燐ドーピング溶液ACCUSPIN P8545を0.5mL添加し溶解させた。得られた溶液を石英基板上に塗布し、サンプルを室温でプラズマを溶媒が揮発するまで継続して照射した。プラズマ照射の条件は内径2mm、外径3mmのガラス製放電管に純度99.99%のヘリウムガスを60リットル/分で流しグローブボックス内にヘリウムを充満し、10kHzの周波数、10kVの電圧を印加した。プラズマ照射後300℃1時間焼成を行い、得られたシリコン膜をかきとり、粒子状で回収し、ESRにより膜中のラジカルを測定した。結果を図12に示す。
上記ESRの測定は、測定条件として磁場:337.5±7.5mT、変調磁場:0.3mT、時定数:0.03秒、マイクロ波出力:1mW、マイクロ波周波数:9.445GHz付近、測定時間は2分とした。
Claims (18)
- 大気圧下において、金属管又は絶縁体管に高電圧電極を取り付けた放電管の内部又は高電圧電極を取り付けた2枚の平板電極の間に導入ガスを流しながら低周波数で高電圧を印加させることにより該放電管の内部又は該平板電極の間に存在する分子をプラズマ化し、そのプラズマを周期律表の第4族乃至第15族に含まれる元素の単体2種以上、該元素を含む化合物2種以上、又は該単体と該化合物との組み合わせである被照射体に照射することを特徴とする周期律表の第4族乃至第15族に含まれる元素同士の異種元素間結合を含む化合物の製造方法。
- 上記異種元素結合を含む化合物が、周期律表の第13族乃至第15族に含まれる元素同士の異種元素間結合を含む化合物である請求項1に記載の製造方法。
- 上記プラズマ又はプラズマにより励起された周囲のガスのラジカルを上記被照射体に照射すると共に、更に上記被照射体に紫外線を照射することを特徴とする請求項1又は請求項2に記載の製造方法。
- 上記異種元素結合を含む化合物が、基板上に被膜として得られる請求項1乃至請求項3のいずれか1項に記載の製造方法。
- 上記被照射体は、上記元素単体、上記化合物、上記元素単体を含む溶液、上記化合物を含む溶液、上記元素単体のガス及び上記化合物のガスからなる群から選択される2種以上である請求項1乃至請求項4のいずれか1項に記載の製造方法。
- 上記被照射体は、その1種が第14族元素を含む化合物であり、他の1種が第4族乃至第15族に含まれる元素単体のガス又は該元素を含む化合物のガスである請求項1乃至請求項5のいずれか1項に記載の製造方法。
- 上記被照射体は、その1種が第14族元素を含む化合物であり、他の1種が第13族元素の単体若しくはその元素を含む化合物又は第15族元素の単体若しくはその元素を含む化合物であり、第14族元素を含む化合物1モルに対して第13族元素の単体若しくはその元素を含む化合物又は第15族元素の単体若しくはその元素を含む化合物を0.2乃至10モルの割合で含むものである、請求項1乃至請求項6のいずれか1項に記載の製造方法。
- 上記異種元素間結合を含む化合物が、Si-Si結合と、Si-B結合又はSi-P結合とを含むものである請求項1に記載の製造方法。
- 上記放電管の内部又は平板電極の間に導入するガスが、ヘリウム、ネオン、アルゴン、クリプトン、キセノン、窒素分子、酸素分子、水素分子、二酸化炭素、一酸化窒素、二酸化窒素、アンモニア、ハロゲン分子、ハロゲン化水素、二硫化硫黄、硫化水素、及び水蒸気からなる群から選ばれる少なくとも1種のガスである請求項1乃至請求項11のいずれか1項に記載の製造方法。
- 上記放電管の内部又は上記平板電極の間に導入するガスが、ヘリウム単独ガス、又はヘリウムと水素分子、酸素分子、窒素分子、二酸化炭素、一酸化炭素、フッ素分子、及び塩素分子からなる群より選ばれる少なくとも1種のガスとの混合ガスである請求項1乃至請求項11のいずれか1項に記載の製造方法。
- 上記2枚の金属又は絶縁体の平板電極は対面し、その一方に高電圧電極を接続し、その他方はアースを接続せず大気アースとするか又はアース電極を接続した構造であり、両電極間にガスを流して電極間に存在する分子をプラズマ化することを特徴とする請求項1乃至請求項13のいずれか1項に記載の製造方法。
- 上記2枚の金属又は絶縁体の平板電極は減圧容器中にあり、減圧後に導入ガスを流し、低いガス圧下で低周波数で高電圧を印加して電極間に存在する分子をプラズマ化することを特徴とする請求項1乃至請求項14のいずれか1項に記載の製造方法。
- 上記金属管の放電管又は金属の平板電極が第4族乃至第14族に含まれる元素単体又はそれを含む混合物からなる請求項1乃至請求項15のいずれか1項に記載の製造方法。
- 上記絶縁体管の放電管又は絶縁体の平板電極が合成高分子、天然高分子、ガラス、又はセラミックスからなる請求項1乃至請求項15のいずれか1項に記載の製造方法。
- プラズマ発生に用いられる電源が10Hz乃至100MHzの周波数、1000V乃至30000Vの出力電圧である、低温でプラズマ照射することを特徴とする請求項1乃至請求項17のいずれか1項に記載の製造方法。
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JP2011547618A JP5574126B2 (ja) | 2009-12-24 | 2010-12-23 | 異種元素結合形成法 |
KR1020127018768A KR101716311B1 (ko) | 2009-12-24 | 2010-12-23 | 이종원소 간 결합을 포함하는 화합물의 제조방법 |
US13/518,712 US20120318662A1 (en) | 2009-12-24 | 2010-12-23 | Method for forming bond between different elements |
US14/691,214 US9994684B2 (en) | 2009-12-24 | 2015-04-20 | Method for forming bond between different elements |
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US13/518,712 A-371-Of-International US20120318662A1 (en) | 2009-12-24 | 2010-12-23 | Method for forming bond between different elements |
US14/691,214 Division US9994684B2 (en) | 2009-12-24 | 2015-04-20 | Method for forming bond between different elements |
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WO2016010038A1 (ja) * | 2014-07-16 | 2016-01-21 | 日産化学工業株式会社 | 濃縮法を用いた環状シランの製造方法 |
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DE102010040231A1 (de) * | 2010-09-03 | 2012-03-08 | Evonik Degussa Gmbh | p-Dotierte Siliciumschichten |
CN102659071B (zh) * | 2012-05-16 | 2015-07-15 | 苏州大学 | 复合阳极键合方法 |
DE102014111781B4 (de) * | 2013-08-19 | 2022-08-11 | Korea Atomic Energy Research Institute | Verfahren zur elektrochemischen Herstellung einer Silizium-Schicht |
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JPH08279495A (ja) * | 1995-02-07 | 1996-10-22 | Seiko Epson Corp | プラズマ処理装置及びその方法 |
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TWI532084B (zh) | 2016-05-01 |
US9994684B2 (en) | 2018-06-12 |
KR101716311B1 (ko) | 2017-03-14 |
KR20120123339A (ko) | 2012-11-08 |
US20150252152A1 (en) | 2015-09-10 |
US20120318662A1 (en) | 2012-12-20 |
TW201137950A (en) | 2011-11-01 |
JP5574126B2 (ja) | 2014-08-20 |
JPWO2011078299A1 (ja) | 2013-05-09 |
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