US20020015803A1 - Method for forming thin film with a gas cluster ion beam - Google Patents

Method for forming thin film with a gas cluster ion beam Download PDF

Info

Publication number
US20020015803A1
US20020015803A1 US09/916,304 US91630401A US2002015803A1 US 20020015803 A1 US20020015803 A1 US 20020015803A1 US 91630401 A US91630401 A US 91630401A US 2002015803 A1 US2002015803 A1 US 2002015803A1
Authority
US
United States
Prior art keywords
substrate
thin film
gas
gas cluster
ions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US09/916,304
Inventor
Makoto Akizuki
Mitsuaki Harada
Atsumasa Doi
Isao Yamada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US09/916,304 priority Critical patent/US20020015803A1/en
Publication of US20020015803A1 publication Critical patent/US20020015803A1/en
Priority to US10/351,555 priority patent/US6797339B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/48—Ion implantation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
    • H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
    • H01L21/02233—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer
    • H01L21/02236—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor
    • H01L21/02238—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor silicon in uncombined form, i.e. pure silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/3165—Inorganic layers composed of oxides or glassy oxides or oxide based glass formed by oxidation
    • H01L21/31654—Inorganic layers composed of oxides or glassy oxides or oxide based glass formed by oxidation of semiconductor materials, e.g. the body itself
    • H01L21/31658—Inorganic layers composed of oxides or glassy oxides or oxide based glass formed by oxidation of semiconductor materials, e.g. the body itself by thermal oxidation, e.g. of SiGe
    • H01L21/31662—Inorganic layers composed of oxides or glassy oxides or oxide based glass formed by oxidation of semiconductor materials, e.g. the body itself by thermal oxidation, e.g. of SiGe of silicon in uncombined form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32105—Oxidation of silicon-containing layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/06—Sources
    • H01J2237/08—Ion sources
    • H01J2237/0812—Ionized cluster beam [ICB] sources

Definitions

  • the present invention relates to a method for forming a thin film on the surface of a substrate with a gas cluster ion beam. More particularly, the present invention relates to a method for forming a thin film by gas cluster ion beam which is a group of reactive substance which is gaseous at the room temperature under the atmospheric pressure. The method is useful for the manufacture of a semiconductor or other electronic devices and for surface reforming of a functional material.
  • a method for forming a thin film by irradiating monatomic or monomolecular ions onto a substrate surface has conventionally been used in practice. This method utilizes a high input energy of several keV because low-energy ion irradiation cannot give an adequate beam because of the space charge effect between ions.
  • a thermal reaction method As a method for forming a thin film by causing reaction between a reactive substance, which is gaseous at the room temperature, and a semiconductor substrate, a thermal reaction method has been developed for forming an oxide or nitride film by heating the substrate to a high temperature in an atmosphere of the reactive substance.
  • the thin film formed by this method has excellent interface and insulation properties, and the method has been industrialized for forming an insulating film or a capacitor insulating film for silicon semiconductor devices.
  • This method requires a low temperature to reduce the diffusion of impurities, which is desirable for integrated circuit devices, the chemical vapor deposition (CVD) method is adopted for this purpose.
  • CVD chemical vapor deposition
  • the plasma CVD method is known as a method for forming a thin film at a low temperature. This method however involves such defects as a large amount of mixed impurities, occurrence of damages to the substrate surface by ions, and difficulty in controlling the film thickness of an ultra-thin film. Furthermore, it is not applicable to a transistor gate insulating film or a capacitor insulating film requiring high quality.
  • the present invention was developed in view of the circumstances as described above, and has an object to provide a method for forming a high-quality ultra-thin film having a smooth interface with the substrate free from a damage at the room temperature, which solves the drawbacks in the conventional methods for forming a thin film.
  • the present invention provides a method for forming a thin film on the surface of substrate with a gas cluster ion beam, which comprises the step of irradiating the surface of a substrate with ions of a gas cluster (which is a massive group of atoms or molecules of a reactive substance taking the gaseous form at room temperature under the atmospheric pressure) to cause a reaction with a substance of the substrate surface, thereby forming a thin film on the substrate surface.
  • ions of a gas cluster which is a massive group of atoms or molecules of a reactive substance taking the gaseous form at room temperature under the atmospheric pressure
  • the invention comprises the steps of using a reactive substance, selected from the group consisting of oxides, nitrides, carbides, mixtures thereof, and mixtures thereof with an inert gas and causing a reaction between a gas cluster ion beam of this substance and a substance of the substrate surface, thereby forming a thin film on the substrate surface.
  • a reactive substance selected from the group consisting of oxides, nitrides, carbides, mixtures thereof, and mixtures thereof with an inert gas
  • the invention provides also a method for forming a thin film based on a gas cluster ion beam, which comprises the steps of irradiating the surface of the substrate with the gas cluster ion beam to form a thin film and at the same time to planarize the surface.
  • FIG. 1 shows transmission type electron microscopic photomicrographs of a section of a silicon substrate by irradiating CO 2 monomer and CO 2 cluster ions onto the substrate surface thereof;
  • FIG. 2 shows an infrared absorption spectrum of a thin film formed by irradiating CO 2 monomer ions and CO 2 cluster ions onto a silicon substrate surface
  • FIG. 6 shows a graph illustrating the relationship between the supply pressure and the cluster beam intensity at various nozzle intensities for nitrogen gas
  • FIG. 7 shows a graph illustrating the relationship between the supply pressure and the cluster beam intensity at various nozzle intensities for argon gas for reference.
  • FIG. 8 shows an infrared absorption spectrum of an oxide film formed by irradiating oxygen (O 2 ) gas cluster onto a silicon substrate surface.
  • the method of the invention comprises generating a gas cluster (which is a massive group of atoms or molecules of a reactive substance which is a gas at room temperature under the atmospheric pressure), irradiating electrons onto this gas cluster to ionize same, and irradiating the thus generated gas cluster ions onto a substrate surface by selecting a beam of a particular size as required.
  • a gas cluster which is a massive group of atoms or molecules of a reactive substance which is a gas at room temperature under the atmospheric pressure
  • Irradiation is accomplished by accelerating the gas cluster ions under an acceleration voltage. Because a cluster usually consists of a group of several hundred atoms or molecules, each atom or molecule is irradiated as an extra-low temperature ion beam with up to several tens of eV and even under an acceleration voltage of 10 KeV. It is therefore possible to form a high-quality ultra-thin film with a very low degree of damage at room temperature. A thin film with the slightest content of impurities can be produced as the impurities are removed from the substrate surface by the effect of the gas cluster ions.
  • Another effective manner of irradiation is to appropriately select the number of component molecules in response to the substrate, the kind of substance of the substrate surface and the desired thin film composition.
  • the cluster itself can be generated by ejecting a pressurized gas through an expansion type nozzle into a vacuum unit, as already proposed by the present inventors.
  • the thus generated cluster can be ionized by irradiating electrons.
  • the gas cluster ions are irradiated onto a substrate surface to planarize the surface and at the same time, the irradiated ions are caused to react with the substance of the substrate surface, thereby permitting formation of a thin film on the substrate surface.
  • the gaseous reactive substances taking a gaseous form at room temperature under the atmospheric pressure include, for example, oxygen, oxides such as CO 2 , CO, N 2 O, NO x , and C x H y O z , carbides, nitrides such as N 2 and NH x , sulfides, halides, hydrides such as AsH x and SiH x , organometallic compounds such as metal carbonyls.
  • the reactive substance is preferably oxygen or a carbon oxide, or a mixture thereof, or a mixture thereof with an inert gas substance, and the thin film formed can be an oxide film.
  • the present invention specifically proposes a method for generating gas cluster ions, which comprises the step of generating a gas cluster by means of a nozzle cooled by a coolant, and ionizing the resultant cluster.
  • FIG. 1 is transmission type electron microscopic photomicrographs of a silicon substrate section when (a) CO 2 monomolecular ions were irradiated onto an silicon substrate at a dose rate of 1 ⁇ 10 16 ions/cm 2 , and (b) CO 2 cluster ions having a number of component molecules (cluster size) of at least 500 were irradiated.
  • FIG. 1( a ) CO 2 monomolecular ions were irradiated under an acceleration voltage of 10 kV onto a silicon (001) substrate.
  • An amorphous silicon layer of a thickness of 19 nm was formed on the substrate surface, and irregularities occurred on the interface between the amorphous layer and the substrate.
  • the amorphous silicon layer is a damaged layer formed when CO 2 ions ejected onto the substrate surface hit atoms of the substrate. These irregularities of the interface and the damaged layer, causing deterioration of semiconductor device properties, must be converted to monocrystalline state. It is however very difficult to achieve complete conversion even through heat treatment at a temperature of at least 800° C.
  • CO 2 cluster ions having a number of component atoms (cluster size) of at least 500 were accelerated under conditions including a dose rate of 1 ⁇ 10 16 ions/cm2 and an acceleration voltage of 10 kV, and then, only clusters of a number of component molecules of at least 500 were irradiated onto a silicon (001) substrate at the room temperature by the retarding-field method.
  • a silicon oxide film having a thickness of 10 nm was formed on the substrate surface, and no damaged layer was observed between the silicon oxide film and the silicon substrate, and the interface in between was very smooth.
  • FIG. 2 is an infrared absorption spectrum of a thin film formed by irradiating CO 2 monomer ions and cluster ions under conditions including an acceleration voltage of 10 kV and a dose rate of 2 ⁇ 10 16 ions/cm onto a silicon substrate surface. While a silicon oxide film only of the order of spontaneous oxide film can be formed by irradiation with CO 2 monomer ions, irradiation with cluster ions permits formation of an oxide film of about 70 A.
  • FIG. 3 illustrates changes in the concentration of Ni impurities as measured with various dose rates of CO 2 ions irradiated onto a silicon substrate, ranging from 0 to 2 ⁇ 10 15 ions/cm 2 .
  • CO 2 cluster ions having a number of component molecules of at least 250 and CO 2 monomer ions were irradiated under an acceleration voltage of 10 kV onto the silicon substrates to which Ni had previously been forcedly deposited to give of 6 ⁇ 10 12 atoms/cm 2 , and changes in the concentration of Ni impurities was measured before and after irradiation through measurement by the total reflection X-ray flourescence analysis method. While the concentration of Ni impurities does not depend upon the extent of dose rate in the irradiation of monomer ions, the concentration of Ni impurities decreases along with the increase in the dose rate in the irradiation of cluster ions.
  • the method of the present invention permitting formation of a clean surface free from defects on the substrate surface, makes it possible to manufacture a high-quality thin film with the slightest content of impurities, useful for a semiconductor circuit device.
  • Table 1 shows, for an SiO 2 film formed on a polycrystalline silicon film irradiated with CO 2 cluster ions under conditions including an acceleration voltage of 10 kV and a dose rate of 5 ⁇ 10 15 ions/cm 2 , the film thickness and the average surface roughness before and after a treatment with fluoric acid solution. The treatment with fluoric acid solution was applied until complete elimination of the SiO 2 film. For comparison purposes, values obtained with a polycrystalline silicon film not irradiated with cluster ions are also shown.
  • the sample not irradiated with cluster ions has an average surface roughness of 37 A, and this value does not vary with the fluoric acid treatment.
  • Irradiation of cluster ions of a size of 250 and 500 reduces the average surface roughness of the polycrystalline silicon film to 7 ⁇ and 18 ⁇ , respectively.
  • an SiO 2 thin film having a thickness of from 8 to 6 nm is formed on the surface of the polycrystalline silicon film, thus forming an SiO 2 thin film simultaneously with planarization.
  • a satisfactory surface planarity is kept with almost no change by the fluoric acid treatment.
  • the irradiation of CO 2 cluster ions permits formation of a silicon oxide film which has a planar surface, with a smooth interface between said film and the silicon substrate, and has a uniform thickness.
  • FIG. 5 is a graph illustrating the relationship between the intensity of oxygen (O 2 ) gas cluster beam and the supply pressure at various nozzle temperatures.
  • FIG. 6 is a graph illustrating such relationship for nitrogen (N 2 ) gas.
  • FIG. 7 illustrates the relationship for Ar gas for reference.
  • d 0 inside diameter of nozzle throat
  • T b boiling point of gas
  • T N ejecting temperature of gas
  • ⁇ ratio of specific heats of gas (specific heat at constant pressure/isometric specific heat).
  • FIG. 8 is an infrared absorption spectrum of a thin film formed by irradiating O 2 cluster ions having a number of component molecules (cluster size) of at least 250 onto an Si substrate surface at room temperature under an acceleration voltage of 4 kV and at a dose rate of 1 ⁇ 10 15 ions/cm 2 . It is clear from FIG. 8 that an oxide film of about 40 A was formed with a lower acceleration voltage and a lower dose rate than the conditions for irradiation of CO 2 cluster ions.
  • Table 2 shows the results of investigation by the photoelectron spectroscopy method of an oxide film formed by irradiating CO 2 cluster ions and O 2 cluster ions under the same irradiating conditions including an acceleration voltage of 4 kV, a cluster size of at least 250, and a dose rate of 1 ⁇ 10 15 ions/cm 2 .
  • the results of investigation on a clean Si substrate not irradiated are also shown for reference.
  • O 2 cluster ions it is possible to form a thicker oxide film as compared with the case of CO 2 cluster ions.

Abstract

A method of forming a thin film on the surface of a substrate such as silicon, in which a gas cluster (which is a massive atomic or molecular group of a reactive substance taking the gaseous form at room temperature under atmospheric pressure) is formed and then ionized, and the cluster ions are then irradiated onto a substrate surface under an acceleration voltage to cause a reaction.
It is possible to form a high quality ultra-thin film having a very smooth interface, without causing any damage to the substrate, even at room temperature.

Description

    FIELD OF THE INVENTION
  • The present invention relates to a method for forming a thin film on the surface of a substrate with a gas cluster ion beam. More particularly, the present invention relates to a method for forming a thin film by gas cluster ion beam which is a group of reactive substance which is gaseous at the room temperature under the atmospheric pressure. The method is useful for the manufacture of a semiconductor or other electronic devices and for surface reforming of a functional material. [0001]
    • PRIOR ART AND PROBLEMS
  • A method for forming a thin film by irradiating monatomic or monomolecular ions onto a substrate surface has conventionally been used in practice. This method utilizes a high input energy of several keV because low-energy ion irradiation cannot give an adequate beam because of the space charge effect between ions. [0002]
  • In this conventional method, however, the use of ions having a large input energy makes it difficult to avoid damage to the substrate surface, and thus deterioration of semiconductor devices has been a major problem. [0003]
  • As a method for forming a thin film by causing reaction between a reactive substance, which is gaseous at the room temperature, and a semiconductor substrate, a thermal reaction method has been developed for forming an oxide or nitride film by heating the substrate to a high temperature in an atmosphere of the reactive substance. The thin film formed by this method has excellent interface and insulation properties, and the method has been industrialized for forming an insulating film or a capacitor insulating film for silicon semiconductor devices. [0004]
  • This method requires a low temperature to reduce the diffusion of impurities, which is desirable for integrated circuit devices, the chemical vapor deposition (CVD) method is adopted for this purpose. [0005]
  • In this case, however, it is necessary to heat the substrate surface to a temperature of at least 400° C., but this results in defects such as a low density of the resultant film as compared with that produced by the thermal reaction method and the presence of many unsaturated bonds on the interface between the substrate and the thin film. [0006]
  • The plasma CVD method is known as a method for forming a thin film at a low temperature. This method however involves such defects as a large amount of mixed impurities, occurrence of damages to the substrate surface by ions, and difficulty in controlling the film thickness of an ultra-thin film. Furthermore, it is not applicable to a transistor gate insulating film or a capacitor insulating film requiring high quality. [0007]
  • In the conventional techniques, as described above, the quality of the resultant thin film deteriorates as the process temperature becomes lower, and it is difficult to obtain an ultra-thin film useful for a hyperfine semiconductor circuit device such as ULSI. [0008]
  • There has consequently been a strong demand for a new method which permits formation of a high-quality thin film at a lower temperature, particularly at room temperature, without the need to heat the substrate and without damaging the substrate surface, as a fundamental technology for use in advanced electronics such as ULSI. [0009]
  • The present invention was developed in view of the circumstances as described above, and has an object to provide a method for forming a high-quality ultra-thin film having a smooth interface with the substrate free from a damage at the room temperature, which solves the drawbacks in the conventional methods for forming a thin film. [0010]
    • SUMMARY OF THE INVENTION
  • The present invention provides a method for forming a thin film on the surface of substrate with a gas cluster ion beam, which comprises the step of irradiating the surface of a substrate with ions of a gas cluster (which is a massive group of atoms or molecules of a reactive substance taking the gaseous form at room temperature under the atmospheric pressure) to cause a reaction with a substance of the substrate surface, thereby forming a thin film on the substrate surface. [0011]
  • More specifically, the invention comprises the steps of using a reactive substance, selected from the group consisting of oxides, nitrides, carbides, mixtures thereof, and mixtures thereof with an inert gas and causing a reaction between a gas cluster ion beam of this substance and a substance of the substrate surface, thereby forming a thin film on the substrate surface. [0012]
  • The invention provides also a method for forming a thin film based on a gas cluster ion beam, which comprises the steps of irradiating the surface of the substrate with the gas cluster ion beam to form a thin film and at the same time to planarize the surface.[0013]
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 shows transmission type electron microscopic photomicrographs of a section of a silicon substrate by irradiating CO[0014] 2 monomer and CO2 cluster ions onto the substrate surface thereof;
  • FIG. 2 shows an infrared absorption spectrum of a thin film formed by irradiating CO[0015] 2 monomer ions and CO2 cluster ions onto a silicon substrate surface;
  • FIG. 3 shows a chart illustrating the relationship between the dose rate of CO[0016] 2 ions to be irradiated and the concentration of impurities in the substrate surface;
  • FIG. 4 shows a diagram illustrating the generation of clusters of various gases by means of a nozzle having cooling means; [0017]
  • FIG. 5 shows a graph illustrating the relationship between the supply pressure and the cluster beam intensity at various nozzle intensities for oxygen gas; [0018]
  • FIG. 6 shows a graph illustrating the relationship between the supply pressure and the cluster beam intensity at various nozzle intensities for nitrogen gas; [0019]
  • FIG. 7 shows a graph illustrating the relationship between the supply pressure and the cluster beam intensity at various nozzle intensities for argon gas for reference; and [0020]
  • FIG. 8 shows an infrared absorption spectrum of an oxide film formed by irradiating oxygen (O[0021] 2) gas cluster onto a silicon substrate surface.
    • DETAILED DESCRIPTION OF THE INVENTION
  • The method of the invention comprises generating a gas cluster (which is a massive group of atoms or molecules of a reactive substance which is a gas at room temperature under the atmospheric pressure), irradiating electrons onto this gas cluster to ionize same, and irradiating the thus generated gas cluster ions onto a substrate surface by selecting a beam of a particular size as required. [0022]
  • Irradiation is accomplished by accelerating the gas cluster ions under an acceleration voltage. Because a cluster usually consists of a group of several hundred atoms or molecules, each atom or molecule is irradiated as an extra-low temperature ion beam with up to several tens of eV and even under an acceleration voltage of 10 KeV. It is therefore possible to form a high-quality ultra-thin film with a very low degree of damage at room temperature. A thin film with the slightest content of impurities can be produced as the impurities are removed from the substrate surface by the effect of the gas cluster ions. [0023]
  • Another effective manner of irradiation is to appropriately select the number of component molecules in response to the substrate, the kind of substance of the substrate surface and the desired thin film composition. [0024]
  • The cluster itself can be generated by ejecting a pressurized gas through an expansion type nozzle into a vacuum unit, as already proposed by the present inventors. The thus generated cluster can be ionized by irradiating electrons. [0025]
  • In the present invention, the gas cluster ions are irradiated onto a substrate surface to planarize the surface and at the same time, the irradiated ions are caused to react with the substance of the substrate surface, thereby permitting formation of a thin film on the substrate surface. [0026]
  • The gaseous reactive substances taking a gaseous form at room temperature under the atmospheric pressure include, for example, oxygen, oxides such as CO[0027] 2, CO, N2O, NOx, and CxHyOz, carbides, nitrides such as N2 and NHx, sulfides, halides, hydrides such as AsHx and SiHx, organometallic compounds such as metal carbonyls.
  • In the present invention, for example, the reactive substance is preferably oxygen or a carbon oxide, or a mixture thereof, or a mixture thereof with an inert gas substance, and the thin film formed can be an oxide film. [0028]
  • In the case of any of the gases including oxygen (O[0029] 2) and nitrogen (N2), the present invention specifically proposes a method for generating gas cluster ions, which comprises the step of generating a gas cluster by means of a nozzle cooled by a coolant, and ionizing the resultant cluster.
  • The invention will be described in further detail by the following of examples. [0030]
    • EXAMPLE 1
  • FIG. 1 is transmission type electron microscopic photomicrographs of a silicon substrate section when (a) CO[0031] 2 monomolecular ions were irradiated onto an silicon substrate at a dose rate of 1×1016 ions/cm2, and (b) CO2 cluster ions having a number of component molecules (cluster size) of at least 500 were irradiated.
  • In FIG. 1([0032] a), CO2 monomolecular ions were irradiated under an acceleration voltage of 10 kV onto a silicon (001) substrate. An amorphous silicon layer of a thickness of 19 nm was formed on the substrate surface, and irregularities occurred on the interface between the amorphous layer and the substrate. The amorphous silicon layer is a damaged layer formed when CO2 ions ejected onto the substrate surface hit atoms of the substrate. These irregularities of the interface and the damaged layer, causing deterioration of semiconductor device properties, must be converted to monocrystalline state. It is however very difficult to achieve complete conversion even through heat treatment at a temperature of at least 800° C.
  • In the case of FIG. 1([0033] b), on the other hand, CO2 cluster ions having a number of component atoms (cluster size) of at least 500 were accelerated under conditions including a dose rate of 1×1016 ions/cm2 and an acceleration voltage of 10 kV, and then, only clusters of a number of component molecules of at least 500 were irradiated onto a silicon (001) substrate at the room temperature by the retarding-field method. A silicon oxide film having a thickness of 10 nm was formed on the substrate surface, and no damaged layer was observed between the silicon oxide film and the silicon substrate, and the interface in between was very smooth.
  • The above-mentioned findings are confirmed also from FIG. 2. FIG. 2 is an infrared absorption spectrum of a thin film formed by irradiating CO[0034] 2 monomer ions and cluster ions under conditions including an acceleration voltage of 10 kV and a dose rate of 2×1016 ions/cm onto a silicon substrate surface. While a silicon oxide film only of the order of spontaneous oxide film can be formed by irradiation with CO2 monomer ions, irradiation with cluster ions permits formation of an oxide film of about 70 A.
    • EXAMPLE 2
  • FIG. 3 illustrates changes in the concentration of Ni impurities as measured with various dose rates of CO[0035] 2 ions irradiated onto a silicon substrate, ranging from 0 to 2×1015 ions/cm2. In this case, CO2 cluster ions having a number of component molecules of at least 250 and CO2 monomer ions were irradiated under an acceleration voltage of 10 kV onto the silicon substrates to which Ni had previously been forcedly deposited to give of 6×1012 atoms/cm2, and changes in the concentration of Ni impurities was measured before and after irradiation through measurement by the total reflection X-ray flourescence analysis method. While the concentration of Ni impurities does not depend upon the extent of dose rate in the irradiation of monomer ions, the concentration of Ni impurities decreases along with the increase in the dose rate in the irradiation of cluster ions.
  • As is clear from these results, in the case of irradiation of cluster ions, it is possible to reduce the concentration of impurities by increasing the dose rate of irradiated ions. The higher impurities-removing effect in the irradiation of cluster ions as compared to the irradiation of monomer (monomolecular) ions is attributable to the fact that, while embedding of impurities adhering to the surface into the interior of the substrate occurs in the irradiation of monomer ions, sputtering from the irradiation onto the substrate preferentially eliminates impurities on the substrate surface in the irradiation of cluster ions. [0036]
  • As described above, the method of the present invention, permitting formation of a clean surface free from defects on the substrate surface, makes it possible to manufacture a high-quality thin film with the slightest content of impurities, useful for a semiconductor circuit device. [0037]
    • EXAMPLE 3
  • Table 1 shows, for an SiO[0038] 2 film formed on a polycrystalline silicon film irradiated with CO2 cluster ions under conditions including an acceleration voltage of 10 kV and a dose rate of 5×1015 ions/cm2, the film thickness and the average surface roughness before and after a treatment with fluoric acid solution. The treatment with fluoric acid solution was applied until complete elimination of the SiO2 film. For comparison purposes, values obtained with a polycrystalline silicon film not irradiated with cluster ions are also shown.
    TABLE 1
    Average surface
    roughness (unit: Å)
    Before After
    Thickness of fluoric fluoric
    SiO2 acid acid
    Kind of sample thin film (nm) treatment treatment
    Sample not irradiated — 37 37
    Sample irradiated with 8 7 9
    cluster ions of
    size of 250
    Sample irradiated with 6 18 20
    cluster ions of
    size of 500
  • The sample not irradiated with cluster ions has an average surface roughness of 37 A, and this value does not vary with the fluoric acid treatment. Irradiation of cluster ions of a size of 250 and 500 reduces the average surface roughness of the polycrystalline silicon film to 7 Å and 18 Å, respectively. At the same time, an SiO[0039] 2 thin film having a thickness of from 8 to 6 nm is formed on the surface of the polycrystalline silicon film, thus forming an SiO2 thin film simultaneously with planarization. A satisfactory surface planarity is kept with almost no change by the fluoric acid treatment. Thus, the irradiation of CO2 cluster ions permits formation of a silicon oxide film which has a planar surface, with a smooth interface between said film and the silicon substrate, and has a uniform thickness.
    • EXAMPLE 4
  • Conditions for generating cluster of various gases were evaluated. As shown in FIG. 4, cooled dry nitrogen gas was passed through a piping ([0040] 2) attached to a nozzle (1) section which was then cooled. This permitted ionization of clusters of gases which had not been possible at room temperature.
  • FIG. 5 is a graph illustrating the relationship between the intensity of oxygen (O[0041] 2) gas cluster beam and the supply pressure at various nozzle temperatures. FIG. 6 is a graph illustrating such relationship for nitrogen (N2) gas. FIG. 7 illustrates the relationship for Ar gas for reference.
  • These results suggest the possibility of determining the degree of easiness of generation of the cluster of a gas applicable in the present invention by means of the following formula: [0042]
  • Easiness of Generation of Cluster [0043]
  • ψ=P 0 ·d 0·(T b /T N)γ/(γ−1)
  • where, [0044]
  • P[0045] 0: gas supply pressure,
  • d[0046] 0: inside diameter of nozzle throat,
  • T[0047] b: boiling point of gas,
  • T[0048] N: ejecting temperature of gas,
  • γ: ratio of specific heats of gas (specific heat at constant pressure/isometric specific heat). [0049]
  • Larger P[0050] 0 or Tb leads to easier generation of clusters.
  • Smaller T[0051] N or γ corresponds to easier generation of clusters.
  • In all the cases described above, various gases were effectively utilized for the formation of thin films. [0052]
    • EXAMPLE 5
  • FIG. 8 is an infrared absorption spectrum of a thin film formed by irradiating O[0053] 2 cluster ions having a number of component molecules (cluster size) of at least 250 onto an Si substrate surface at room temperature under an acceleration voltage of 4 kV and at a dose rate of 1×1015 ions/cm2. It is clear from FIG. 8 that an oxide film of about 40 A was formed with a lower acceleration voltage and a lower dose rate than the conditions for irradiation of CO2 cluster ions.
    • EXAMPLE 6
  • Table 2 shows the results of investigation by the photoelectron spectroscopy method of an oxide film formed by irradiating CO[0054] 2 cluster ions and O2 cluster ions under the same irradiating conditions including an acceleration voltage of 4 kV, a cluster size of at least 250, and a dose rate of 1×1015 ions/cm2. The results of investigation on a clean Si substrate not irradiated are also shown for reference. By using O2 cluster ions, it is possible to form a thicker oxide film as compared with the case of CO2 cluster ions. It is also clear that the relative intensity of emission spectrum from Cls core level of the oxide film formed by the irradiation of O2 clusters is of the same order as that for a substrate not irradiated and the carbon content is almost nil, even with the largest film thickness. When presence of residual carbon in the film is not desired, it is suggested to be effective to use O2 cluster ions to obtain a thicker oxide film.
    TABLE 2
    Raw material gas Oxide film
    of irradiated thickness Relative intensity
    cluster ions (unit: A) of C1s signal
    O2 40 31
    CO2 18 44
    Substrate not 8 29
    irradiated
  • According to the present invention, as described above in detail, it is possible to form a high-quality reactive ultra-thin film, with no damage to the substrate, having a very smooth interface, even at the room temperature, by irradiating cluster ions of a reactive substance onto the substrate surface to cause reaction. [0055]

Claims (11)

What is claimed is:
1. A method for forming a thin film on the surface of a substrate with a gas cluster ion beam, which comprises the step of irradiating the surface of a substrate with ions of a gas cluster (which is a massive group of atoms or molecules of a reactive substance taking the gseous form at room temperature under atmospheric pressure) to cause a reaction with the surface of a substrate and thereby form a thin film on the substrate surface.
2. A method as claimed in claim 1, wherein the said reactive substance is oxygen, an oxide, nitrogen, a nitride, a carbide, a sulfide, a halide, a hydride, an organo metallic compound, a mixture thereof or a mixture thereof with an inert gas.
3. A method as claimed in claim 1, wherein the gas cluster ions are selected in terms of the number of component molecules.
4. A method as claimed in 1, wherein impurities present on the substrate are removed by the irradiation with the gas cluster ion beam, thereby forming a thin film with a low content of impurities.
5. A method as claimed in claim 1, wherein the substrate surface is planarized (made flat) by the irradiation with the gas cluster ions, at the same time as the formation of the thisn film.
6. A method as claimed in claim 1, wherein the thin film formed is an oxide.
7. A method as claimed in claim 1, wherein the substrate is silicon.
8. A method as claimed in claim 1, wherein the reactive substance is oxygen, an oxide of carbon, an oxide of nitrogen, a mixture thereof, or a mixture thereof with a rare (inert) gas, and the thin film formed is an oxide film.
9. A method as claimed in claim 1, wherein the gas cluster is generated by supplying a pressurized gas to an expansion type nozzle cooled by a coolant.
10. A method as claimed in claim 1, which includes the steps of
(i) forming a gas cluster from a substance which is reactive with the surface of the substrate and is a gas at room temperature and atmospheric pressure,
(ii) ionizing the gas cluster, and
(iii) irradiating the surface of the substrate with a beam of gas cluster ions.
11. A method for generating gas cluster ions, which comprises the steps of generating a gas cluster with an expansion type nozzle cooled by a coolant and ionizing the resultant cluster.
US09/916,304 1994-09-06 2001-07-30 Method for forming thin film with a gas cluster ion beam Abandoned US20020015803A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US09/916,304 US20020015803A1 (en) 1994-09-06 2001-07-30 Method for forming thin film with a gas cluster ion beam
US10/351,555 US6797339B2 (en) 1994-09-06 2003-01-27 Method for forming thin film with a gas cluster ion beam

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP213078/1994 1994-09-06
JP21307894 1994-09-06
JP06844595A JP3352842B2 (en) 1994-09-06 1995-03-27 Thin film formation method by gas cluster ion beam
JP68445/1995 1995-03-27
US52392295A 1995-09-06 1995-09-06
US75708896A 1996-11-26 1996-11-26
US94666397A 1997-10-07 1997-10-07
US09/916,304 US20020015803A1 (en) 1994-09-06 2001-07-30 Method for forming thin film with a gas cluster ion beam

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US94666397A Continuation 1994-09-06 1997-10-07

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US10/351,555 Continuation US6797339B2 (en) 1994-09-06 2003-01-27 Method for forming thin film with a gas cluster ion beam

Publications (1)

Publication Number Publication Date
US20020015803A1 true US20020015803A1 (en) 2002-02-07

Family

ID=26409669

Family Applications (2)

Application Number Title Priority Date Filing Date
US09/916,304 Abandoned US20020015803A1 (en) 1994-09-06 2001-07-30 Method for forming thin film with a gas cluster ion beam
US10/351,555 Expired - Fee Related US6797339B2 (en) 1994-09-06 2003-01-27 Method for forming thin film with a gas cluster ion beam

Family Applications After (1)

Application Number Title Priority Date Filing Date
US10/351,555 Expired - Fee Related US6797339B2 (en) 1994-09-06 2003-01-27 Method for forming thin film with a gas cluster ion beam

Country Status (2)

Country Link
US (2) US20020015803A1 (en)
JP (1) JP3352842B2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060118731A1 (en) * 2004-12-03 2006-06-08 Canon Kabushiki Kaisha Gas cluster ion beam emitting apparatus and method for ionization of gas cluster
WO2005079318A3 (en) * 2004-02-14 2006-10-05 Epion Corp Methods of forming doped and un-doped strained semiconductor and semiconductor films by gas-cluster ion irradiation
US20120104347A1 (en) * 2010-11-02 2012-05-03 Micron Technology, Inc. Method of forming a chalcogenide material, methods of forming a resistive random access memory device including a chalcogenide material, and random access memory devices including a chalcogenide material

Families Citing this family (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3770970B2 (en) * 1996-08-28 2006-04-26 昭和ゴム株式会社 Surface treatment method of medical article by argon gas cluster ion beam
WO2000026431A1 (en) * 1998-11-03 2000-05-11 Epion Corporation Gas cluster ion beams for formation of nitride films
US20030206837A1 (en) 1998-11-05 2003-11-06 Taylor Charles E. Electro-kinetic air transporter and conditioner device with enhanced maintenance features and enhanced anti-microorganism capability
US6176977B1 (en) 1998-11-05 2001-01-23 Sharper Image Corporation Electro-kinetic air transporter-conditioner
US20050210902A1 (en) 2004-02-18 2005-09-29 Sharper Image Corporation Electro-kinetic air transporter and/or conditioner devices with features for cleaning emitter electrodes
US7695690B2 (en) 1998-11-05 2010-04-13 Tessera, Inc. Air treatment apparatus having multiple downstream electrodes
US6375790B1 (en) 1999-07-19 2002-04-23 Epion Corporation Adaptive GCIB for smoothing surfaces
US6416820B1 (en) 1999-11-19 2002-07-09 Epion Corporation Method for forming carbonaceous hard film
US6498107B1 (en) 2000-05-01 2002-12-24 Epion Corporation Interface control for film deposition by gas-cluster ion-beam processing
FR2850400B1 (en) * 2003-01-29 2005-03-11 Soitec Silicon On Insulator CARBURIZING SILICON SURFACES USING A GAS AMMONIUM ION BEAM
US7906080B1 (en) 2003-09-05 2011-03-15 Sharper Image Acquisition Llc Air treatment apparatus having a liquid holder and a bipolar ionization device
US7724492B2 (en) 2003-09-05 2010-05-25 Tessera, Inc. Emitter electrode having a strip shape
US7767169B2 (en) 2003-12-11 2010-08-03 Sharper Image Acquisition Llc Electro-kinetic air transporter-conditioner system and method to oxidize volatile organic compounds
US20060018809A1 (en) 2004-07-23 2006-01-26 Sharper Image Corporation Air conditioner device with removable driver electrodes
US7799683B2 (en) * 2004-11-08 2010-09-21 Tel Epion, Inc. Copper interconnect wiring and method and apparatus for forming thereof
JP4515931B2 (en) * 2005-02-01 2010-08-04 三菱電機株式会社 Thin film semiconductor manufacturing method and thin film transistor manufactured by the manufacturing method
US7504135B2 (en) * 2005-02-03 2009-03-17 Samsung Electronics Co., Ltd Method of fabricating a manganese diffusion barrier
US7833322B2 (en) 2006-02-28 2010-11-16 Sharper Image Acquisition Llc Air treatment apparatus having a voltage control device responsive to current sensing
JP4850127B2 (en) * 2007-05-30 2012-01-11 三洋電機株式会社 Solid electrolytic capacitor and manufacturing method thereof
US7824741B2 (en) 2007-08-31 2010-11-02 Micron Technology, Inc. Method of forming a carbon-containing material
US7749849B2 (en) * 2007-12-18 2010-07-06 Micron Technology, Inc. Methods of selectively oxidizing semiconductor structures, and structures resulting therefrom
US7905199B2 (en) * 2008-06-24 2011-03-15 Tel Epion Inc. Method and system for directional growth using a gas cluster ion beam
WO2010008700A2 (en) * 2008-06-24 2010-01-21 Tel Epion Inc. Method and system for growing a thin film using a gas cluster ion beam
US9103031B2 (en) * 2008-06-24 2015-08-11 Tel Epion Inc. Method and system for growing a thin film using a gas cluster ion beam
US20090314963A1 (en) * 2008-06-24 2009-12-24 Tel Epion Inc. Method for forming trench isolation
US8313663B2 (en) 2008-09-24 2012-11-20 Tel Epion Inc. Surface profile adjustment using gas cluster ion beam processing
US8981322B2 (en) * 2009-02-04 2015-03-17 Tel Epion Inc. Multiple nozzle gas cluster ion beam system
US20100193898A1 (en) * 2009-02-04 2010-08-05 Tel Epion Inc. Method for forming trench isolation using gas cluster ion beam processing
US8097860B2 (en) * 2009-02-04 2012-01-17 Tel Epion Inc. Multiple nozzle gas cluster ion beam processing system and method of operating
US7968422B2 (en) * 2009-02-09 2011-06-28 Tel Epion Inc. Method for forming trench isolation using a gas cluster ion beam growth process
US8226835B2 (en) * 2009-03-06 2012-07-24 Tel Epion Inc. Ultra-thin film formation using gas cluster ion beam processing
US7982196B2 (en) * 2009-03-31 2011-07-19 Tel Epion Inc. Method for modifying a material layer using gas cluster ion beam processing
US8877299B2 (en) * 2009-03-31 2014-11-04 Tel Epion Inc. Method for enhancing a substrate using gas cluster ion beam processing
US8048788B2 (en) * 2009-10-08 2011-11-01 Tel Epion Inc. Method for treating non-planar structures using gas cluster ion beam processing
US20110084214A1 (en) * 2009-10-08 2011-04-14 Tel Epion Inc. Gas cluster ion beam processing method for preparing an isolation layer in non-planar gate structures
US8237136B2 (en) * 2009-10-08 2012-08-07 Tel Epion Inc. Method and system for tilting a substrate during gas cluster ion beam processing
US8338806B2 (en) 2010-05-05 2012-12-25 Tel Epion Inc. Gas cluster ion beam system with rapid gas switching apparatus
US8173980B2 (en) 2010-05-05 2012-05-08 Tel Epion Inc. Gas cluster ion beam system with cleaning apparatus
JP5236687B2 (en) * 2010-05-26 2013-07-17 兵庫県 Surface treatment method and surface treatment apparatus
US8481340B2 (en) 2010-06-16 2013-07-09 Tel Epion Inc. Method for preparing a light-emitting device using gas cluster ion beam processing
US8440578B2 (en) * 2011-03-28 2013-05-14 Tel Epion Inc. GCIB process for reducing interfacial roughness following pre-amorphization
US9540725B2 (en) 2014-05-14 2017-01-10 Tel Epion Inc. Method and apparatus for beam deflection in a gas cluster ion beam system
KR102347960B1 (en) 2015-02-03 2022-01-05 삼성전자주식회사 Conductor and method of manufacturing the same
US10541172B2 (en) 2016-08-24 2020-01-21 International Business Machines Corporation Semiconductor device with reduced contact resistance
US11450506B2 (en) 2020-04-24 2022-09-20 Tel Manufacturing And Engineering Of America, Inc. Pattern enhancement using a gas cluster ion beam

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2631881C2 (en) 1975-07-18 1982-11-25 Futaba Denshi Kogyo K.K., Mobara, Chiba Method for manufacturing a semiconductor component
WO1987002026A1 (en) 1984-05-28 1987-04-09 Shuhara Akira Process for producing silicon dioxide film
US4559096A (en) 1984-06-25 1985-12-17 The United States Of America As Represented By The United States Department Of Energy Method of precisely modifying predetermined surface layers of a workpiece by cluster ion impact therewith
JPS6353259A (en) 1986-08-22 1988-03-07 Mitsubishi Electric Corp Method for forming thin film
JPH01136102A (en) 1987-11-24 1989-05-29 Mitsui Toatsu Chem Inc Polarizing film
US4882023A (en) 1988-03-14 1989-11-21 Motorola, Inc. Method and system for producing thin films
DE3809734C1 (en) 1988-03-23 1989-05-03 Helmut Prof. Dr. 7805 Boetzingen De Haberland
JPH03266803A (en) * 1990-03-16 1991-11-27 Mitsubishi Electric Corp Formation of mirror for short wavelength
JP2662321B2 (en) 1991-05-31 1997-10-08 科学技術振興事業団 Surface treatment method using ultra-slow cluster ion beam
US5350607A (en) 1992-10-02 1994-09-27 United Technologies Corporation Ionized cluster beam deposition of sapphire
JPH06224156A (en) 1992-11-13 1994-08-12 Hitachi Ltd Surface treating method and apparatus
US5527731A (en) 1992-11-13 1996-06-18 Hitachi, Ltd. Surface treating method and apparatus therefor
US5584739A (en) * 1993-02-10 1996-12-17 Futaba Denshi Kogyo K.K Field emission element and process for manufacturing same
US6486068B2 (en) * 1998-01-08 2002-11-26 Toyoda Gosei Co., Ltd. Method for manufacturing group III nitride compound semiconductor laser diodes
US6375790B1 (en) * 1999-07-19 2002-04-23 Epion Corporation Adaptive GCIB for smoothing surfaces
JP3345638B2 (en) * 1999-11-11 2002-11-18 独立行政法人産業技術総合研究所 Transparent conductive film and method for producing the same
US6416820B1 (en) * 1999-11-19 2002-07-09 Epion Corporation Method for forming carbonaceous hard film
JP2003521812A (en) * 1999-12-06 2003-07-15 エピオン コーポレイション Gas cluster ion beam smoother
US6498107B1 (en) * 2000-05-01 2002-12-24 Epion Corporation Interface control for film deposition by gas-cluster ion-beam processing
AU2001273276A1 (en) * 2000-07-10 2002-01-21 Epion Corporation Improving effectiveness of medical stents by gcib
EP1303866B1 (en) * 2000-07-10 2009-12-09 TEL Epion Inc. System and method for improving thin films by gas cluster ion be am processing
JP4796737B2 (en) * 2000-07-10 2011-10-19 エクソジェネシス コーポレーション Improvement of artificial hip joint by GCIB

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005079318A3 (en) * 2004-02-14 2006-10-05 Epion Corp Methods of forming doped and un-doped strained semiconductor and semiconductor films by gas-cluster ion irradiation
US20060118731A1 (en) * 2004-12-03 2006-06-08 Canon Kabushiki Kaisha Gas cluster ion beam emitting apparatus and method for ionization of gas cluster
US7365341B2 (en) 2004-12-03 2008-04-29 Canon Kabushiki Kaisha Gas cluster ion beam emitting apparatus and method for ionization of gas cluster
US7855374B2 (en) 2004-12-03 2010-12-21 Canon Kabushiki Kaisha Gas cluster ion beam emitting apparatus and method for ionization of gas cluster
US20120104347A1 (en) * 2010-11-02 2012-05-03 Micron Technology, Inc. Method of forming a chalcogenide material, methods of forming a resistive random access memory device including a chalcogenide material, and random access memory devices including a chalcogenide material
US8679914B2 (en) * 2010-11-02 2014-03-25 Micron Technology, Inc. Method of forming a chalcogenide material and methods of forming a resistive random access memory device including a chalcogenide material
US9130164B2 (en) 2010-11-02 2015-09-08 Micron Technology, Inc. Resistive random access memory devices, and related semiconductor device structures

Also Published As

Publication number Publication date
US20030143340A1 (en) 2003-07-31
JP3352842B2 (en) 2002-12-03
JPH08127867A (en) 1996-05-21
US6797339B2 (en) 2004-09-28

Similar Documents

Publication Publication Date Title
US6797339B2 (en) Method for forming thin film with a gas cluster ion beam
US6797334B2 (en) Method for forming gas cluster and method for forming thin film
US6124158A (en) Method of reducing carbon contamination of a thin dielectric film by using gaseous organic precursors, inert gas, and ozone to react with carbon contaminants
EP0536664B1 (en) A method for forming a thin film
CN1331199C (en) UV prtreatment process for ultra-thin oxynitride for formation of silicon nitridefilms
US7981810B1 (en) Methods of depositing highly selective transparent ashable hardmask films
US8003174B2 (en) Method for forming dielectric film using siloxane-silazane mixture
Yu et al. The adsorption of PH3 on Si (100) and its effect on the coadsorption of SiH4
US6825130B2 (en) CVD of porous dielectric materials
JPH0578844A (en) Amorphous thin film having solid lubricity and its production thereof
JPH09508757A (en) Method of forming fluorinated silicon oxide layer using plasma enhanced chemical vapor deposition
US20090087586A1 (en) Method of forming silicon nitride films
Ishihara et al. Laser-assisted chemical vapor deposition of titanium nitride films
Yamada et al. Process Technologies for Ta/SiC X‐Ray Masks
US4522886A (en) Method of ion beam synthesis of thin silicon nitride films and resulting articles
Itoh et al. Low-dielectric-constant nonporous fluorocarbon films for interlayer dielectric
JP3795423B2 (en) Thin film formation method by gas cluster ion beam
Koshino et al. Chemical states of bromine atoms on SiO2 surface after HBr reactive ion etching: Analysis of thin oxide
US20220375747A1 (en) Flowable CVD Film Defect Reduction
JPH1064849A (en) Method and apparatus for manufacturing thin film
Seidler et al. Low Temperature Selective Area Chemical Vapor Deposition of Gold Films: Growth and Characterization
Otani et al. Effects of electron-cyclotron-resonance oxygen plasma irradiation on properties of insulator/Ge-semiconductor interfaces prior to germanium nitride formation
US11367614B2 (en) Surface roughness for flowable CVD film
JP3039880B2 (en) Carbon film formation method
Yamamoto et al. Growth and effects of remote-plasma oxidation on thin films of HfO 2 prepared by metal-organic chemical-vapor deposition

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION