Carbon cluster film having electrical conductivity and method of preparing the same

Abstract: Disclosed herein is a stable carbon cluster film having precisely controlled electrical conductivity, which will not be deteriorated in a short period in air. Such a carbon cluster film having conductivity is formed by introducing an impurity into a thin film of fullerenes by ion implantation. The fullerenes include C₆₀, C₇₀ or the like.

Description: BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a novel carbon cluster film, and more particularly, it relates to a carbon cluster film which can stably maintain its electrical conductivity and a method of preparing the same. Description of the Background Art There has recently been proposed a technique of doping a thin film of a carbon cluster such as C 60 or C 70 , so-called "fullerene", consisting of a certain number of carbon atoms linking with each other in the form of spheres such as soccer balls or spheroids such as Rugby balls, with an alkaline metal by vacuum diffusion, as described in articles by Haddon, R. C. et al., Nature, Vol. 350, March 28, 1991, pp. 320 to 322 and by Hebard, A. F. et al., Nature, Vol. 350, April 18, 1991, pp. 600 to 601. The former one of these articles reports that electrical conductivity values of 500 S/cm and 100 S/cm are obtained in C 60 thin films which are doped with potassium (K) and rubidium (Rb) by vacuum diffusion respectively, for example. On the other hand, the latter article reports that a C 60 thin film which is doped with potassium by vacuum diffusion exhibits superconductivity at a critical temperature Tc of 18 K from the result of microwave absorption and measurement of magnetization and at a critical temperature Tc of 16 K from the result of measurement of resistance. It is also reported that a C 60 thin film which is doped with rubidium exhibits superconductivity at a critical temperature Tc of 30 K. There is such a possibility that a thin film which has arbitrary conductivity ranging from a insulator to a superconductor can be prepared from the aforementioned carbon cluster by adjusting the amount of a doped alkaline metal. However, a thin film which is doped with an alkaline metal by vacuum diffusion in the aforementioned manner is so unstable in air that its electrical conductivity is lowered in a short period. This is conceivably because the alkaline metal itself is highly reactive with oxygen and water as is well known in the art, and a compound generated by reaction with the carbon cluster which is doped with the alkaline metal by vacuum diffusion is so unstable that the same tends to react with oxygen and water being contained in the air, for example, to cause decomposition. In the aforementioned vacuum diffusion, further, it is difficult to precisely control electrical conductivity since the amount of the alkaline metal which is doped in the thin film cannot be strictly controlled. It was also proposed to make n-type and p-type fullerene films by doping them with impurity atoms, such as He by ion implantation (Scientific American, Vol. 265, No. 4, p. 32-41, October 1991). Further, ion implantation was applied to introduce argon ions into diamond-like carbon (DLC) films (Extended Abstracts, Spring Meeting, Los Angeles, CA, 89/1, Abstract No. 86, page 127, May 7-12, 1989). However, DLC comprises a completely different structure compared to a fullerene cluster. SUMMARY OF THE INVENTION The present invention has been proposed in consideration of the aforementioned circumstances, and an object thereof is to provide a stable carbon cluster film having precisely controlled electrical conductivity, which will not be deteriorated in a short period under the atmosphere. The present invention therefore concerns a carbon cluster thin film and its method of preparation as described in claims 1 and 3 respectively. In order to solve the aforementioned problem, a carbon cluster film according to the present invention is formed by introducing an impurity by ion implantation into a thin film which consists essentially of a carbon cluster having a π electron conjugate system. According to the present invention, it is possible to obtain a carbon cluster film which is more stable in air than a conventional film with no possibility of deterioration of its electrical conductivity in a short period, even if an alkaline metal is ion-implanted as an impurity. When an element which is more stable than an alkaline metal is ion-implanted as an impurity, stability of the carbon cluster film having conductivity is further improved. According to the present invention, the carbon cluster film having an electrical conductivity is thus improved in stability conceivably because the impurity which is ion-implanted into the carbon cluster thin film in a high energy state forms a stable compound with the carbon cluster on the exterior of the aforementioned fullerene. The reason why the stable compound is generated, however, has not been fully found out. There is also a possibility that the impurity enters the inside of the fullerene spheroid to form the air stable compound. In the ion implantation, it is possible to extremely precisely control the amount of the impurity which is implanted into the thin film by electrically monitoring the total amount of the implanted impurity ions, while it is also possible to implant the impurity into the thin film to a desired depth by controlling the acceleration voltage of the ion beam, whereby the electrical conductivity of the carbon cluster film can be precisely controlled. Further, the aforementioned ion implantation has such an advantage that it is possible to freely control electrical conductivity in an arbitrary position of the carbon cluster thin film by controlling the region to which the ion beam is applied. The carbon cluster can be used from any carbon cluster having a π electron conjugate system expressed as C 2n , where 10 ≦ n ≦ 100, in addition to the aforementioned C 60 and C 70 . Such a carbon cluster is prepared by burning hydrocarbon at a high temperature, or by subjecting graphite or carbon to resistance heating, arc discharge, laser beam heating, electron beam evaporation, magnetron sputtering or the like, under an inert gas atmosphere, and then, if necessary, by purifying the soot obtained by the above processes to high purity of at least 99.9 % by solvent extraction, a column chromatograph, or sublimation. In order to form a thin film from the carbon cluster, a well known thin film forming method such as vacuum plating, a cluster-ion beam method, a molecular beam epitaxial (MBE) method, sputtering, a Langmuir-Blodgett's film method, solvent coating or the like may be applied to a raw material which is prepared from microcrystalline powder of a purified carbon cluster. When such a thin film forming method is combined with a well known patterning method such as masking, etching or printing, it is possible to form a carbon cluster thin film having a prescribed pattern in response to the shape of an element, a circuit or the like. Further, it is also possible to form a carbon cluster thin film having a crystalline structure through epitaxy. The thin film is not particularly restricted in thickness but any arbitrary thickness can be selected in response to the application of the thin film. A substrate to be provided with the thin film is not particularly restricted but the same may be prepared from any arbitrary substrate such as glass, quartz, diamond, a semiconductor such as silicon, GaAs, InP or ZnSe, or a ceramic material such as MoS, BN or Aℓ 2 O 3 . The impurity can be implanted into the aforementioned thin film by well known ion implantation employing a general ion implantation apparatus. The ion-implanted impurity preferably serves as a donor or an acceptor for the carbon cluster. An impurity serving as a donor may be prepared from an alkaline metal element such as Li, Na, K or Rb, an alkaline earth metal element such as Be, Mg, Ca, Sr or Ba, a transition element such as Fe, Co or Ni, a lanthanide element, an actinide element, an element belonging to the group IIIb of the periodic table such as B, Aℓ, Ga or In, or an element belonging to the group IVb of the periodic table such as Ge, Sn or Pb, while an impurity serving as an acceptor may be prepared from an element belonging to the group Vb of the periodic table such as N, P, As or Sb, a chalcogen element such as O, S, Se or Te, or a halogen element such as F, Cℓ, Br or I. The dose amount of the impurity into the thin film may be arbitrarily adjusted in response to target conductivity of the carbon cluster film, as hereinabove described. If the dose amount is too large, however, carbon cluster molecules may be cut or broken to deteriorate the film quality. Therefore, it is preferable to set a favorable upper limit of the dose amount in a range not causing such decomposition etc. in response to the thickness of the carbon cluster film, the atomic weight of the ion-implanted impurity element, the implantation voltage and the like. When the carbon cluster thin film has a thickness of 100-1000 nm (1000 to 10000 Å) and N + ions are implanted at an implantation voltage of 100 KeV, for example, the upper limit of the dose amount per 1 cm 2 of the thin film is preferably 10 16 ions. The resistivity of the carbon cluster film obtained after such ion implantation, the value of which is influenced by the activation factor of the implanted element, is set at a value of not more than 10 4 Ω·cm. The acceleration voltage of the ion beam determines the depth of implantation of the impurity, as hereinabove described. While the acceleration voltage and the depth of implantation are varied with the atomic weight of the ion-implanted impurity etc., an acceleration voltage of about 200 KeV at the maximum may be applied in order to ion-implant the impurity into the overall carbon cluster thin film having a thickness of 100-1000nm (1000 to 10000 Å), for example. According to the present invention, as hereinabove described, it is possible to obtain a stable carbon cluster film having precisely controlled arbitrary electrical conductivity ranging from a semiconductor to a conductor. Further, there is such a possibility that a superconducting film can be formed by appropriately selecting the type of the impurity and ion implantation conditions, as described in the aforementioned articles. In the inventive carbon cluster film, three-dimensional and isotropic (C 60 ) or anisotropic (C 70 ) characteristics can be expected, as anticipated from the steric structure of the carbon cluster expressed as C 2n , particularly the structure of C 60 or C 70 . In other words, it is possible to prepare a film which is controlled in dimensionality in relation to electric characteristics, optical characteristics, electro-optic characteristics and the like by selecting the shapes of C 2n molecules. According to the present invention, C 60 , C 70 , C 76 , C 78 , C 80 , C 82 , C 84 or C 96 can be preferably employed as a carbon cluster having a fullerene structure. According to the present invention, further, it is possible to form a p-type or n-type semiconductor with implantation of an acceptor or a donor, by selecting the type of the ion-implanted impurity. Thus, it is possible to easily manufacture an element of p-n junction or p-i-n junction by combining formation of the carbon cluster film and ion implantation. When the carbon cluster thin film is formed by a vapor phase method such as vacuum evaporation, the element can be more easily manufactured since all the aforementioned steps can be carried out as dry processes in a vacuum. In order to form a p-n junction element, for example, a carbon cluster thin film may be formed on a substrate so that an impurity serving as a donor is ion-implanted into this thin film to form a p-type semiconductor layer, and another carbon cluster thin film is formed thereon so that an impurity serving as an acceptor is ion-implanted into this film to form an n-type semiconductor layer. In order to form a p-i-n junction element, on the other hand, an insulating layer may be formed between such p-type and n-type semiconductor layers. Also when a carbon cluster film exhibiting superconductivity is employed, it is possible to manufacture an arbitrary superconducting element by combining formation of a carbon cluster film and ion implantation. For example, SIS junction can be formed by interposing an insulating layer between two superconducting layers, while SMS junction can be formed by interposing a metal layer between such superconducting layers. The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is now described on the basis of Examples. Example 1 A commercially available C 60 /C 70 carbon cluster was purified through a column chromatograph with a neutral alumina serving as a column packing material and a mixed solvent containing hexane and benzene in the ratio of 95:5, and thereafter vacuum-dried at 200°C to obtain a C 60 carbon cluster of 99.9 % in purity in the form of microcrystalline powder. Then, this C 60 carbon cluster was evaporated on a surface of a glass substrate of 10 mm by 20 mm by 0.5 mm by vacuum evaporation, to form a transparent pale yellow carbon cluster thin film of 500 nm (5000 Å) in thickness. The vacuum evaporation was carried out under conditions of a degree of vacuum of 1,3·10 -3 to 1,3·10 -6 Pa (10 -5 to 10 -8 Torr), an evaporation source temperature of 300°C and an evaporation source-to-substrate distance of 7.5 cm. Then N + ions were implanted into the aforementioned thin film by ion implantation under a condition of an acceleration voltage of 100 KeV, to measure relation between the dose amount and the resistivity. As the result, it was recognized that the resistivity of the carbon cluster film was reduced as the dose amount of the N + ions was increased, as shown in Table 1. When the as-obtained carbon cluster film was left under the atmosphere at the room temperature, the resistivity of the film remained unchanged for at least one month. Dose Amount (ions/cm 2 ) 10 11 10 13 10 15 Resistivity (Ω·cm) 10 1 10 -2 Example 2 A C 60 carbon cluster was obtained by carrying out purification similarly to Example 1. The as-obtained carbon cluster was deposited on a quartz glass substrate by ion beam deposition, to form a transparent pale yellow C 60 carbon cluster thin film having a thickness of about 300 nm (3000 Å), under conditions of a degree of vacuum of 1,3·10 -4 to 1,3·10 -5 Pa (10 -6 to 10 -7 ) Torr, an evaporation source temperature of 300°C, an ionization voltage of 25 V and an acceleration voltage of 100 V. Then, B ions were implanted into the carbon cluster thin film under a condition of an acceleration voltage of 200 KeV with a density of 10 15 /cm 2 , to obtain a carbon cluster thin film having a resistivity of 10 -1 Ω·cm. The resistivity of the carbon cluster thin film was stable for at least one month in the atmosphere at the room temperature. Example 3 Commercially available microcrystalline powder of purified C 60 of more than 99 % in purity was washed with tetrahydrofuran. Most part of the tetrahydrofuran was removed by centrifugation from the powder, to obtain a purified carbon cluster by vacuum drying at 200°C. The as-obtained carbon cluster was employed as an evaporation source, to form C 60 carbon cluster thin films of 100 nm (1000 Å) in thickness on a ZnSe (100) substrate, a GaAs (100) substrate and an Si (111) substrate by molecular beam epitaxy respectively. These thin films were formed under conditions of a degree of vacuum of 1,3·10 -6 to 1,3·10 -7 Pa (10 -8 to 10 -9 ) Torr, an evaporation source (K cell) temperature of 200 to 300°C, a film forming rate of 0,01 nm/s (0.1 Å/s) and a substrate temperature of 25°C. The as-obtained thick films were subjected to X-ray diffraction (XRD), whereby clear fcc crystal peaks were observed. In such X-ray diffraction, the carbon cluster thin films formed on the ZnSe, GaAs and Si substrates exhibited fcc(111) peak having FWHM (full width at half maximum) of 0.93°, 1.15° and 1.26° respectively. Then, a four-probe lead for measuring resistance was mounted on the C 60 thin film which was formed on the GaAs (100) substrate with Ag paste, and thereafter Rb ions were implanted into this film at an acceleration voltage of 20 KeV. The resistivity of the ion-implanted thin film was measured in a vacuum at 25°C, whereby a value of 2 x 10 -2 Ω·cm was obtained. Then, the substrate provided with the thin film was left in dry air, to be subjected to investigation of resistance change. No resistance change was recognized in relation to the thin film at least for 6 hours. On the other hand, a C 60 thin film which was doped with Rb by vacuum diffusion in place of ion implantation exhibited a resistivity of 5 x 10 -3 Ω·cm in a vacuum at the room temperature. When this thin film was left in dry air, however, the resistance immediately exceeded 10 8 Ω, to exhibit an insulating property. Through the aforementioned experiments, it has been clarified that the inventive carbon cluster thin film which is doped with an impurity by ion implantation is remarkably stable in conductivity as compared with a conventional doped thin film. According to the present invention, an impurity is implanted into a carbon cluster thin film by ion implantation, whereby it is possible to obtain a stable carbon cluster film having precisely controlled electrical conductivity, which will not be deteriorated in a short period in air. Thus, there is such a possibility that the inventive carbon cluster film can be applied to various fields of a semiconductor device, a superconducting device and the like by appropriately selecting the type of the implanted impurity and implantation conditions and suitably combining the ion implantation step with another step, to attain a high industrial value.

Claims: A carbon cluster thin film having an electrical conductivity, and consisting essentially of a carbon cluster having a fullerene structure having a π electron conjugate system, characterized by an impurity introduced into said thin film by ion implantation for maintaining said electrical conductivity outside the vacuum in atmospheric air and by a resistivity of not more than about 10 4 Ω cm at room temperature, wherein said impurity consists of one or more elements selected from the group of alkaline metals, alkaline earth metals, elements belonging to the groups III, IV and V of the periodic table, chalcogen elements, halogen elements, and transition elements. A carbon cluster film in accordance with claim 1, wherein said carbon cluster is prepared from one or more materials selected from a group of C 60 , C 70 , C 76 , C 78 , C 80 , C 82 , C 84 and C 96 . A carbon cluster film in accordance with claim 1, having a crystalline structure. A carbon cluster film in accordance with claim 1, being formed on a substrate. A method of preparing an electrical conductive carbon cluster film having a resistivity of not more than 10 4 Ω cm at room temperature, comprising: a step of forming a thin film consisting essentially of a carbon cluster having a fullerene structure having a π electron conjugate system; and a step of introducing an impurity into said thin film by ion implantation for stably maintaining said electrical conductivity outside the vacuum in atmospheric air, wherein said impurity consists of one or more elements selected from the group of alkaline metals, alkaline earth metals, elements belonging to the groups III, IV and V of the periodic table, chalcogen elements, halogen elements, and transition elements. A method of preparing a carbon cluster film in accordance with claim 5, wherein said thin film is formed by vacuum plating, ion beam deposition or molecular beam epitaxy. A method of preparing a carbon cluster film in accordance with claim 5, wherein said thin film has a crystalline structure. A method of preparing a carbon cluster film in accordance with claim 5, wherein said thin film is formed on a substrate.

Inventors: KUGAI HIROKAZU, OHKURA KENGO, OKUDA NBUYUKI, UEBA YOSHINOBU, KUGAI, HIROKAZU, OHKURA, KENGO, OKUDA, NOBUYUKI, UEBA, YOSHINOBU, Kugai, Hirokazu, c/o Osaka Works of Sumitomo, Ohkura, Kengo, c/o Osaka Works of Sumitomo, Okuda, Nbuyuki, c/o Osaka Works of Sumitomo, UEBA, YOSHINOBU, C/O OSAKA WORKS OF SUMITOMO
Applicants: SUMITOMO ELECTRIC INDUSTRIES, SUMITOMO ELECTRIC INDUSTRIES, LIMITED
Application year: 1992
Main classification: C23C14
IPC codes: C23C14, C30B23, C30B31