JPS6230512B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an amorphous semiconductor member that can withstand high temperatures and a method for manufacturing the same. In summary, as described in U.S. Patent No. 4177473 (corresponding to Japanese Patent Application Laid-Open No. 143180/1977) filed on May 18, 1977, the amorphous semiconductor member of the present invention has the following characteristics:
The present invention has superior properties compared to crystalline semiconductor members such as doped crystalline silicon and germanium, and compensation and doped glow discharge amorphous semiconductors such as amorphous silicon and germanium. or a wide range of uses including current generating devices such as solar radiators, current controlling devices such as PN junction devices including diodes, transistors, etc., and uses resulting from the use of the principles of the present invention. Many other applications of are possible. As set forth in the aforementioned U.S. Pat. No. 4,177,473, the amorphous semiconductor components of the present invention can be formed from multiple elements, including alloys, that provide the desired energy gap and electrical activation. Semiconductor components that can be selected and designed to produce an amorphous matrix having substantially any desired structural and electronic arrangement with energy and desired physical, thermal and optical properties The electronic arrangement can be substantially and separately modified to modify the electroactive energy to provide a semiconductor member with desired electrical properties while providing a semiconductor member with desired electrical properties.
Amorphous semiconductor components are synthetically produced, need not be produced from a melt, need not be dependent on stoichiometry, and are not bound by crystalline form or prohibitions. This means that the physical, chemical,
This means that there is a range of completely new material combinations that can be designed to optimize the desired material properties with respect to thermal and electrical properties. According to the present invention, the amorphous semiconductor component can withstand high temperatures and have good strength properties, and in this respect the present invention is superior to the invention of the aforementioned U.S. Pat. No. 4,177,473. Progress is being made. Crystalline semiconductors were put into practical use and formed the basis of a huge business as well as the basis of a great scientific establishment. This essentially changes the intrinsic germanium and especially silicon crystals into extrinsic materials, converting them into p
or n-type. This includes a substantially pure crystalline material in which a small amount of dopant is added as a substitutional impurity to increase the electrical conductivity and control it to either p or n type. was carefully introduced. This was done by growing individual single crystals in carefully controlled conditions and by doping them with extremely small critical amounts of dopants in carefully controlled conditions. . In such crystalline semiconductors, purification,
The technologies of purification, compounding, mixed crystal growth, and doping became central to industry and made it possible to manufacture computers as well as transistor radios. This revolutionary fact arises from the well-known scientific basis: crystals from groups of the periodic table such as silicon and germanium, dopant materials from groups such as boron as acceptors, and dopant materials from groups of the periodic table such as boron as acceptors; It was associated with the introduction of group dopant materials such as arsenic. In connection with the aforementioned doped crystalline semiconductors, the manufacturing process is complex, time consuming, and expensive. There are also many problems with the yield of such doped crystalline semiconductors. They need to have an energy gap determined by the particular crystal used. Moreover, due to the single crystal nature of such semiconductors, there are size limitations and devices of large dimensions cannot be provided. Because of the aforementioned difficulties with such crystalline semiconductors (doped silicon and germanium crystals), the industry has turned to the use of amorphous silicon and germanium semiconductors to replace crystalline semiconductors.
Work in the field of amorphous materials has been discouraging to those familiar with the field of crystalline materials. Such people have come to know that amorphous materials have unique electronic switching and structural memory effects, but amorphous materials are essentially intrinsic and therefore cannot be effectively fabricated into transistors, etc. Because it could not be done, there was no impact on the mainstream of semiconductor science and technology. Moreover, such work has generally been unproductive because stable amorphous semiconductors of amorphous silicon or germanium have not been obtained. Amorphous silicon or germanium (Group) has microvoids and dangling bonds that are unbonded, and usually 4 Heavily coordinated. Such localized states remain in amorphous silicon or germanium with or without doping, and they are subjected to deposition conditions and conditions such as annealing, including temperature and other ambient conditions. This changes its characteristics and makes it sufficiently unstable that it cannot be used as a reliable semiconductor transistor or the like. To minimize the aforementioned problems associated with amorphous silicon and germanium, the WESpear and PGLe Comber at the Carnegie Physics Laboratory at the University of Dundee, Dundee, Scotland, are designed to minimize the aforementioned problems with amorphous silicon and germanium, which are very similar to intrinsic crystalline silicon or germanium. The purpose is to reduce the localized states within their energy gap in order to make crystalline materials more extrinsic and to
For the purpose of substitutively doping said amorphous materials with suitable dopants, as in the case of doping crystalline materials to produce shaped materials, in 1975 "Solid State Communications", Volume 17, Vol.
As reported in the paper published on pages 1193-1196,
“Substitutional Doping of Amorphous
For n-type, phosphine (PH ₃ ) gas is added to silane (SiH ₄ ) gas, and for p-type, diborane (B ₂ H ₆ ) gas is used. Pre-mixed gas mixture rf
This was accomplished by glow discharge deposition passed through a reaction tube, which was decomposed by a glow discharge and deposited on the substrate at a high substrate temperature of approximately 500-600°K. The materials so deposited on the substrate are silicon and 30
% hydrogen (silicon hydride), and the reactant gas consists of SiH ₄ and substituted phosphorus or boron with a dopant concentration between about 5×10 ⁻⁶ and 10 ⁻² by volume. As mentioned above, amorphous silicon and also germanium are usually quadruple-coordinated and have microvacancies and dangling bonds that provide localized states within the energy gap. The hydrogen in the silane combines with the many dangling bonds of silicon during glow discharge deposition, reducing or minimizing the density of dangling bonds and microvoids in the deposited amorphous material, and increasing the density of dangling bonds in the energy gap. In order to compensate for the localized state, an amorphous material that is closest to the corresponding crystalline material is produced, which is the purpose of producing an amorphous material. The dopants phosphorus from the group elements to give the n-type and boron from the group elements to give the p-type, obtained from phosphine and diborane, respectively, are added to the doping of the single crystal during glow discharge deposition. Similarly, it has been incorporated into amorphous depositions in a quadruple coordination manner as a substitutional impurity for silicon in amorphous materials. Although the density of states in the energy gap of glow-discharge amorphous silicon is substantially reduced, especially at the Fermi level, two relatively dense state bumbs are evident in the remaining dangling bond density. Remaining within the associated energy gap, they are located approximately 0.4 eV apart substantially below the conduction band E _c and above the valence band E _v . When glow discharge amorphous silicon is doped with phosphorus or boron, the Fermi level is thought to move up or down, but an insufficient amount of active sites move the Fermi level past either bump. influenced to do. Therefore, the activation energy for doped glow discharge amorphous silicon did not drop below 0.2 eV. This result also indicates a theoretical limit on the open circuit voltage of the P-N junction of doped glow-discharge amorphous silicon, since the internal field cannot exceed the separation of the Fermi levels in the p- and n-type regions. . In addition, the remaining activation energy limits the room temperature DC conduction of the doped glow discharge amorphous silicon, which has a large sheet resistance when the material is made into wide area arrays.
This resistance is not helped by the lower carrier mobility, which is about 0/10 ⁵ less than crystalline silicon. As in the case of silicon crystal semiconductors,
Glow discharge amorphous semiconductors using silicon have a substantially defined energy gap. The aforementioned glow discharge amorphous silicon, which is compensated by hydrogen to closely resemble crystalline silicon and doped in a similar manner to doping crystalline silicon, all done during glow discharge deposition, can be In this respect, it has properties inferior to those of doped crystalline silicon, and cannot be effectively used in place of doped crystalline silicon. Such glow discharge amorphous silicon has problems such as insufficient adhesion to the substrate on which it is deposited and cracking. As mentioned above, instead of compensating an amorphous material to closely resemble a crystalline material and doping the amorphous material in the manner of doping a crystalline material, the present invention and the invention of the aforementioned U.S. Pat. No. 4,177,473 directly relates to disordered amorphous materials, takes into account the differences between amorphous and crystalline materials rather than their similarities, and arbitrarily determines the energy gap between the structural order and electronic arrangement of amorphous materials. A simple technical system that can be used to select or process many elements of each group of the periodic table, allowing their active energies to be manipulated arbitrarily and separately for optimal design, and which can be formed into a solid amorphous state. It has to do with making it a reality. Accordingly, in accordance with the present invention and the invention of the above-mentioned application, there are substantially no crystal symmetry or single energy gap limitations as known in the art. In summary, the present invention and the aforementioned U.S. Pat.
In accordance with the invention of No. 4,177,473, an amorphous semiconductor material is a solid amorphous matrix having a structural arrangement with local rather than long-range order and an electronic arrangement with energy gaps and electroactive energies. is formed. A solid amorphous matrix of amorphous semiconductor material is formed as a layer or film deposited onto a substrate, such as by sputtering, at various temperatures, preferably below the crystalline or glass transition temperature, and which produces structural and electronic alignment. is frozen and remains at least in a quasi-equilibrium state.
Although amorphous semiconductor materials have many bonding options, the bonding of amorphous semiconductor materials containing elements to a solid amorphous matrix is primarily by covalent bonding, which provides a very strong bond; The original state and its energy gap are substantially maintained. As used herein, the normal structural bonds that normally characterize prepared amorphous materials
structural bonding is a state in which each atom forms an optimal number of bonds, such as covalent bonds, that uniquely corresponds to the cohesive energy of the amorphous solid. The energy gap E (eV) is the energy difference between the states at the top of the valence band and the bottom of the conduction band. It is usually measured optically and is often referred to as the optical band gap. The energy gap is essentially determined by the solid amorphous semiconductor material forming the amorphous matrix and its structural arrangement. Solid amorphous semiconductor materials can have a wide spectrum of localized states within the energy gap, including bonded and non-bonded states, where such states are characterized by anomalous or defective electronic alignment. (defect electronic configurations) and affect the Fermi level and electroactive energy of semiconductor materials. Such defective electronic arrangements may include substitutional impurities, vacancies, interstitial voids, dislocations, etc. that occur primarily in crystalline solids due to periodic binding. In solid amorphous materials, periodic constraints within crystalline materials can result in three-dimensional electron orbital relationships that are normally prohibited in crystalline materials. Other defective electron arrangements, especially in amorphous semiconductor materials, include microvacancies and dangling bonds, dangling bonds and nearest neighbor interactions, lone pairs, lone pair to lone pair interactions, isolated Interaction between electron pairs and nearest neighbor atoms, valence electron change pairs, donor or coordination bonds, charge compensation, polyvalence, lone pair compensation, hybridization, three-center bond, π bond, complexing, etc. , all of which act to pinning and influence the Fermi level within the material's energy gap to control conduction processes in the semiconductor material. The localized states and electroactive energy within the energy gap depend on the structural arrangement of the amorphous matrix, the nearest neighbor atomic relationships of elements within the amorphous matrix, the aforementioned defect electron arrangement, and the electrical activity within the amorphous matrix. associated with physical activity centers. Electric active energy E
〓(eV) is the energy difference between the Fermi level and the nearest adjacent band edge (valence band or conduction band), which, if unchanged, generally corresponds to 1/2 of the energy gap. To further summarize, the present invention and the aforementioned U.S. Pat.
In accordance with the invention of '4177473, a modifying material is added to the aforementioned solid amorphous matrix of amorphous semiconductor material to modify the electronic arrangement by forming electronic states in the energy gap; It changes and realigns the localization within the energy gap. As a result, the Fermi level of the energy gap is shifted rather than pinned, and the electroactive energy of the amorphous matrix is substantially altered to change the electrical conductivity at room temperature and above. The modifier added to the amorphous matrix is in an amount greater than or equal to about 35% by volume of the dopant typically used to dope crystalline semiconductors or to dope the aforementioned glow discharge amorphous silicon. is also possible. The modifier is not just a dopant, but a true modifier that modifies the electronic arrangement of the amorphous matrix (including localized states) and its electroactive energy. The modification material is added to the amorphous matrix by co-depositing the modification material and the semiconductor material onto a relatively cool substrate. The modifying material is therefore preferably added during the formation of the amorphous matrix at a temperature below the crystalline or glass transition temperature, or at a temperature below the melting temperature of the semiconductor material. Co-deposition of the modified material and the amorphous semiconductor material can be accomplished, for example, by co-sputtering the materials onto the substrate simultaneously. The modifying substance is then added to the amorphous semiconductor material while the solid amorphous matrix is being formed, with the important result that the doping is not based on substitution. When a modifying substance is applied to a predominantly semiconducting material at a temperature above its glass transition temperature or its melting temperature, it acts as a substituent element within the amorphous matrix giving it an intrinsic structure, such as by covalent bonding within the amorphous matrix. It is combined with. Furthermore, the electrical changes are
The change in electroactive energy is not as substantial as that provided by the present invention and the inventions of the aforementioned applications. Alternatively, the modifying material is added to the amorphous matrix of the amorphous semiconductor material at a temperature below the glass transition or melting temperature of the amorphous matrix, such that the amorphous matrix remains substantially intact. If the transition is minimal, if not stopped, then the structural arrangement of the amorphous matrix, and the energy and
There will be a change in the gap. Preferably, the modifier is introduced into the amorphous matrix while the amorphous matrix is in at least a quasi-equilibrium state, but if the modifier is added, different changes occur in the electronic arrangement of the amorphous matrix. To provide this, the amorphous matrix is placed in a non-equilibrium state, for example by applying an electric field or radiant energy. The modifier added to the amorphous matrix of the amorphous semiconductor material can be added, for example, by Coulomb forces, or by covalent, dative or coordinate bonds, interaction of the electron orbits of the amorphous matrix and the modifier, etc. It is located and held by a variety of physical and chemical means by a wide range of bonds, including various combinations thereof. When a modifying material is added to a solid amorphous matrix in the manner described above, it is observed in many different fields, including nearest neighbor relationships, elemental space, bond angles and strengths, band and Including charge and localized states in the gap, microvacancies, dangling bonds, lone pairs, etc., if the modified material is introduced into the bulk above the glass transition temperature or melting temperature of the amorphous material. And it is not recognized in the various places mentioned above. The modifier can also seek out such fields and form desired electronic states within the energy gap (and can also modify the localized state within the energy gap) in order to change the activation energy. Accordingly, the electronic arrangement of the amorphous matrix can be easily changed. If the amorphous matrix has localized states, microvacancies, dangling bonds, lone pairs, etc. from the beginning, the modification material added to the amorphous matrix will also have the ability to form new electronic states. Additionally, the amorphous matrix can be rendered at least partially inert. The modifying substance added to the amorphous host matrix has electron orbitals that interact with the amorphous host matrix to substantially change the electroactive energy of the amorphous host.・
Forming electronic states within the energy gap that substantially alter the electronic arrangement of the matrix. Modified substances include elements with sp electron orbitals, nickel, tungsten, vanadium, copper, zinc, molybdenum,
It can include transition metal elements with d-electron orbitals, such as rhodium or iron, and rare earth elements, such as gatlinium or erbium, which have d- and f-electron orbitals. At least not atomically sufficient d
Transition metals with electronic orbitals are generally preferred. This is because such d-orbitals have a wider range of interaction possibilities with the amorphous host matrix than elements with sp-orbitals. By appropriate selection of these elements and the relative amounts of selected elements, or by utilizing additional elements within the amorphous matrix, structural alignment can be achieved at any desired energy level. - Can be selected and designed to provide electronic arrays with gaps. Such an amorphous matrix of solid amorphous semiconductor material can therefore be manufactured to provide the desired energy gap therein. Modified materials with d-electron orbits, such as nickel, dungsten, etc., can be modified by intersputtering, etc., in the manner described above, with exceptional results obtained especially with group and group elements and transition metals.
It can be easily added to an amorphous matrix of solid amorphous semiconductor material. The addition of these modifiers to an amorphous matrix does not affect the structural coupling or its energy gap of the structural arrangement of the amorphous matrix, even if some of the modifiers are initially combined in a structural bond. not give. However, such additions change the electroactive energy of the localized states or electroactive centers in the energy gap and the electronic arrangement to a substantial extent that transforms the amorphous matrix from an intrinsic to an extrinsic semiconductor. influence In this relationship, the modifying material interacts with the solid amorphous material of the amorphous matrix to form electronic states or electroactive centers, which means that the electronic orbits of the modifying material and the amorphous matrix including interactions. Thus, the addition of modifiers to amorphous semiconductor material within an amorphous matrix has a small effect on structural alignment and energy gaps, but has a wide range of effects on electronic alignment and activation energy. I can do it. The electronic states or electronic active centers so provided include creating electrical charge centers. Abnormal or defective electronic arrangement (DEC) at the same time
Any localized states or electroactive centers present in the amorphous matrix, such as those produced by, can be made substantially inactive, and any electronic states or electroactive centers imparted by the modifier can be rendered substantially inactive. Essentially defines the electronic state and electroactive energy within the energy gap. The density of localized states or electroactive centers within the amorphous matrix of an amorphous semiconductor material varies substantially with the added modifying material, and the relatively dense bumps form a glow discharge amorphous. It does not remain in the energy gap between the Fermi level and the conduction band or valence band as described above in high quality silicon. the result,
The Fermi level is significantly shifted within the energy gap toward the conduction or valence band by the modifier, resulting in a large change in the electroactive energy.
The amount of modifier added to the amorphous matrix is
The amount of change in localized state and formation of electronic states in the energy gap and the amount of change in electroactive energy are determined. Thus, the energy gap and electronic states within the electroactive energy can also be predetermined and shaped to match desired electrical properties. In fundamentally lone-pair amorphous semiconductor materials, including Group and Group elements, the electronic arrangement primarily involves lone pairs and their interactions with their nearest neighbors; These materials are generally structurally compensated to be intrinsic, have very few if any dangling bonds, have no microvacancies, and are spin compensated.
It is considered an “ideal” amorphous material. Lone pairs of electrons and their interactions with their nearest neighbors form electron orbits or defective electron arrays, and the added modifiers form electronic states or electroactive centers in the energy gap. It interacts with and changes the nearest neighbor atoms in the amorphous matrix, many of which involve interaction of electron orbits of the modified material with defective electron arrangements in the amorphous matrix. In fundamentally tetrahedrally bonded amorphous semiconductor materials containing group elements, localized states or electroactive centers within the energy gap are particularly
including electron orbitals or defective electron configurations such as hedral bonds and dangling bonds, where the modified material is used to change the localized state and form new electronic states or electroactive centers within the energy gap. , interacts with the aforementioned defects in the amorphous matrix, many of which involve interaction of the electron orbits of the modifying material with defective electron alignments and dangling bonds in the amorphous matrix. In amorphous semiconductor materials containing group boron, the localized states or electroactive centers in the energy gap include especially electron orbitals or three-center bonds in which two electrons It is shared by three electrons in one covalent bond and a deformable non-bonded state, which is mostly an inverted similar lone pair state. The modified material interacts with such semiconducting material within the amorphous matrix to form new electronic states or electroactive centers in the energy gap, many of which have a non-contact relationship with the electronic orbits of the modified material. Involves interactions with three centers and other bonds within the crystalline matrix. The electron orbits of the modified material interact with localized states or electroactive centers within the energy gap of the amorphous host matrix material to modify the electronic arrangement of the amorphous host matrix.
In accordance with the principles of the invention, the amorphous semiconductor members of the invention have desired physical and electrical properties, such as a desired energy gap (bumper gap)
(eV), electrical conductivity at room temperature σ _RT (Ωcm) ^-1 , electroactive energy E〓(eV), Seebeck coefficient S
(V/° C.), p or n conductivity type, and can be designed or manufactured to provide an amorphous semiconductor member having temperature conductivity. By appropriately designing the parameters of the Seebeck coefficient and the electrical conductivity, which should be relatively high, and the temperature conductivity, which should be relatively low, an effective thermoelectric generation device can be easily manufactured. A first object of the present invention is to provide an amorphous semiconductor component that can withstand high temperatures and have good strength properties, so that said component can It can operate at higher temperatures and withstand the physical rigors of commercial use. In summary, the amorphous semiconductor member of the present invention is an amorphous semiconductor material containing multiple elements such as boron, carbon,
It contains at least one element with a small atomic weight such as nitrogen or oxygen, and has a structural arrangement that has local order rather than long-range order consisting of multiple elements, and electrons that provide an energy gap and electroactive energy. a solid amorphous host matrix having a structure in which the electrons of the amorphous host matrix are attached to the amorphous host matrix and interact with the amorphous host matrix and at room temperature and above. and a modification material consisting of an element selected from the group consisting of nickel and tungsten, having electron orbits forming an electronic state in the energy gap that substantially changes the arrangement, It involves a substantial change. The amorphous host matrix of an amorphous semiconductor material is usually intrinsically conductive, and a modifying substance added to the amorphous host matrix can change said matrix to extrinsically conductive. can. Modifiers added to the amorphous host matrix can substantially change its electroactive energy and therefore the electrical conductivity of the semiconductor component at room temperature and above. It can also substantially change the Seebeck coefficient of the semiconductor component. The amorphous semiconductor material of the amorphous host matrix may also include at least two of the aforementioned low atomic weight elements. Examples of amorphous semiconductor materials forming an amorphous host matrix are boron (B), carbon (C), boron and nitrogen (BN), boron and carbon ( _B4C ), silicon and nitrogen (Si), among others. ₃ N ₄ ), silicon and carbon (SiC), silicon and oxygen (SiO ₂ ), tellurium and oxygen (TeC ₂ ), etc. Modifying substances include, for example, transition metals as mentioned above,
may include. Since the amorphous semiconductor material in the amorphous host matrix contains elements of small atomic weight (light elements), it can withstand high temperatures, e.g.
It can operate at high temperatures of 600℃ and higher. In addition, when the amorphous host matrix contains elements of small atomic weight (light elements), the amorphous semiconductor component has good structural strength and strength properties, which is especially true when the amorphous host matrix contains elements of small atomic weight (light elements). This is the case when the matrix contains a composite of multiple low atomic weight elements such as those mentioned above, rather than a single element. In this regard, the aforementioned low atomic weight elements (light elements) within the amorphous host matrix provide strong covalent bonding forces and high melting point temperatures corresponding to high crystal and glass transition temperatures. Crystal forces act to change an amorphous structure into a crystalline structure, which requires the movement of atoms and the transition from an amorphous state to a crystalline state, and at the crystal and glass transition temperatures of the amorphous structure. arise. The strong bonding strength and high melting temperature and correspondingly high crystalline and glass transition temperatures of the amorphous host matrix of the present invention containing low atomic weight elements minimize the movement of its atoms and thus the amorphous host matrix.・The matrix can withstand high temperatures and have good strength properties,
The amorphous state can be maintained. Other embodiments of the amorphous semiconductor components of the present invention include amorphous semiconductor materials that are primarily tetrahedral-bonded, with structural alignment having local order rather than long-range order, and energy gaps and electroactivity. silicon or germanium formed in a solid amorphous host matrix with an energizing electronic arrangement. It also contains modifiers that are added to the amorphous matrix in a primarily non-substitutional manner, are in an amount greater than the dopant amount, and contain elements of low atomic weight, including for example boron or carbon, in addition to the amorphous The amorphous host matrix has electron orbitals that form electronic states in the energy gap that interact with the amorphous host matrix and substantially alter the electronic arrangement of the amorphous host matrix at room temperature and above. Also, in embodiments of the present invention, the amorphous host matrix of the amorphous semiconductor material is typically of intrinsic conductivity, and the modification material added to the amorphous host matrix makes the matrix extrinsically conductive. can be changed to Modifiers added to the amorphous host matrix can substantially change its electroactive energy and therefore the electrical conductivity of the semiconductor component at room temperature and above. . It can also substantially change the Seebeck coefficient of the semiconductor component and/or its conductivity type. Because the modified material added to the amorphous host matrix contains low atomic weight elements (light elements), the resulting modified semiconductor device can also withstand high temperatures and can operate at room temperature and higher temperatures. , can have good strength properties. The present invention will be explained in detail below with reference to the illustrated embodiments. Referring to FIG. 1, one type of semiconductor device of the present invention is designated generally at 10. It is an amorphous semiconductor member 11 deposited on a substrate 12.
The substrate is preferably made of an insulating material such as glass. The amorphous semiconductor member 11 is formed in a solid amorphous host matrix having a structural arrangement with local rather than long-range order and an electronic arrangement with energy gaps and large electroactive energies. It includes an amorphous semiconductor material 13. Amorphous semiconductor material 11 is also added to the amorphous matrix and amorphous semiconductor material 13
The modified material 14 is substantially homogeneously mixed therein. The amorphous semiconductor member may also include electrodes 16 and 17 provided for electrical connection. Amorphous semiconductor member 11 is preferably formed by interdeposition of an amorphous semiconductor material and a modifier material, such as by intersputtering. Reciprocal sputtering can be accomplished with conventional RF sputtering systems, such as those manufactured and sold by RDMAthis. Here, the cathode or target is formed from a semiconductor material that is bonded to a conventional aluminum backing plate and deposited on the substrate 12.
The modification material is also immobilized on the target semiconductor material. The substrate 12 is carried by a holder a distance from the target of about 3.5 cm for a 3.5" diameter cathode and about 3 cm for a 1" diameter cathode. The sputtering machine initially uses approximately 6×10 ^-6 Torr (mmHg) to provide a background vacuum pressure.
evacuated to a somewhat lower vacuum pressure. Argon is flowed into the machine to provide an operating pressure of about 5 x 10 ^-3 Torr as determined by the Pirani vacuum gauge reading, giving the machine an actual vacuum pressure of about 7 x 10 ^-3 Torr. The surface of the cathode or target and the surface of the modifier are first cleaned for about 30 minutes by sputtering against the shutter of the machine adjacent to the substrate. The shutter is then opened and the target semiconductor material and the modified material on the target are intersputtered onto the substrate. Both the cathode or target and the holder for the substrate are water cooled, and during the sputtering operation the temperature is at a low value below the melting, crystallizing or glass transition temperature of the material. The rf power of the machine has a frequency of about 13.56MHz and a voltage of about 1000V, and the power is about 50-70W.
Utilizes a 3.5" diameter cathode or target. Deposition rate depends on the material being sputtered;
The deposition time is varied to obtain the desired deposition thickness. The thickness of the amorphous semiconductor component co-deposited with the modifying material varies from a few hundred angstroms to about 5 microns, depending on the manner in which the material is placed. The semiconductor material and the modifier material are deposited on the substrate in amorphous form. The amount of modifying material that is applied substantially homogeneously to the amorphous semiconductor material to form the amorphous semiconductor component is generally determined by the area of the modifying material piece applied to the cathode or target semiconductor material. Ru.
Therefore, the desired proportion of modifier added to the amorphous semiconductor material can be controlled accordingly. The deposited semiconductor can be annealed if necessary. As shown in FIG. 1, electrodes 16 and 17 are
They are provided at intervals along the amorphous semiconductor member 11 in order to receive electrical properties along the longitudinal direction of the semiconductor member 11 . For example, device 10 of FIG. 1 may be a thermoelectric generator such that when one end of the device is heated to a higher temperature than the other end, thermal power is transferred to spaced electrodes 16 and 17. Appears within the semiconductor member to be removed between the two. Another embodiment of the invention is shown at 10A in FIG. 2, in which electrodes 16 and 17 respond to the electrical properties of amorphous semiconductor member 11 through their thickness rather than along their length. It differs from the device 10 of FIG. 1 in that it is located on the opposite side of the amorphous semiconductor member 11, as shown in FIG. In this regard, the metal electrode 16 is first deposited on the substrate 12, and then the amorphous semiconductor member 11 is deposited. An amorphous semiconductor component 11 containing an amorphous semiconductor matrix 13 with a homogeneously applied modifier 14 may be formed and deposited in a manner similar to the amorphous semiconductor component 11 of FIG. The amorphous semiconductor member 11 can be formed by mutual sputtering as described above. After the amorphous semiconductor member 11 is formed, a metal electrode 17 is deposited as shown in FIG. As an example, the amorphous semiconductor device 10A of FIG. 2 is used as a thermoelectric generator by heating the electrode 17 above the temperature of the electrode 16 so as to generate thermal power in the amorphous semiconductor member 11. Yes, electrode 1
6 and 17 are used to extract thermal power. As another example, metal electrode 17 may be a transparent metal to allow light to pass through. The transparent electrode 17 is associated with the semiconductor component and is such as to provide a Schottky barrier between the electrode and the semiconductor component 11.
Light, such as solar energy, can photoelectrically generate voltages and currents that can be extracted by electrodes 16 and 17 at the Schottky barrier. Amorphous semiconductor material 11 may be p- or n-type, and as shown in FIG. 3, device 22 generally includes two layers of amorphous semiconductor material 11, one p-type and the other p-type. It is n-type. These two layers form a pn junction 23 between them. Accordingly, device 22 may include a pn junction type device for current control, or the like. The curve in FIG. 5 shows one of the features of the present invention, and the curve shows the electrical conductivity σ [Ωcm] ^-1 with respect to the reciprocal of temperature 1000/T [〓] ^-1 . The unaltered amorphous semiconductor material within the amorphous host matrix
It has a structure with a gap E ₀₄ and a large electroactive energy E 〓, and since such an unchanged material is intrinsic, its electroactive energy E 〓 is approximately 1/2 of the energy gap E ₀₄ . Here, for example, the energy gap is 1.5 eV and the electroactive energy E is 0.75 eV, as shown by curve 35. When the modifying substance is added to the amorphous semiconductor material, it is accompanied by a decrease in the electroactive energy E〓, for example, until the electroactive energy E〓 of 0.02 eV reaches the value shown by curve 37 in FIG. Depending on the amount of modification material added, the intrinsic unmodified semiconductor material can be
It is optionally converted or modified into an extrinsic substance having a stable extrinsic level, indicated by the dashed line 36 in the figure. These stable extrinsic levels make the electrical conductivity at room temperature (and above) σ _RT [Ωcm] ^-1
It increases as shown by the intersection of curves 35, 36 and 37 in the figure with room temperature line 38. Therefore by adding selected amounts of modifying substances,
The intrinsic, unaltered amorphous semiconductor material can optionally be converted into an extrinsic material, which, at room temperature and above, decreases the desired electroactive energy E and changes added to the amorphous semiconductor material. It has a stable extrinsic level with a desired electrical conductivity σ _RT that increases with the amount of material. A wide range of activation energies and electrical conductivities can be engineered into amorphous semiconductor components to meet desired electrical parameters. The curve of FIG. 4 illustrates another feature of the invention; the curve shows the absorption coefficient logα [cm] ^-1 versus the energy gap E [eV]. Energy gap E ₀₄ has an absorption coefficient of amorphous semiconductor material of 10 ⁴
[cm] Equals the energy that is ^-1 . For an unchanged semiconductor material as considered with respect to curve 35 of FIG. 5, the energy gap E ₀₄ is approximately 1.50 eV as shown by curve 39 of FIG.
For modified semiconductor materials as discussed with respect to curve 37 of FIG. 5, the energy gap E ₀₄ is approximately 1.45 eV as shown by curve 40 of FIG. Therefore, the active energy E〓 and its electrical conductivity σ
There is a significant difference between _RT and energy gap between unmodified and modified semiconductor material.
It can be seen that there is almost no difference in E ₀₄ . This is probably due to the fact that adding a modifying substance to an amorphous semiconductor material has little effect on the structural alignment of the amorphous semiconductor matrix and the energy gap of its electrical alignment. A wide design range of active energy and electrical conductivity is therefore applicable to amorphous semiconductor components, which is important for maintaining the physical properties, including thermal and optical properties, of the amorphous semiconductor material. This can be done without substantially changing the arrangement and energy gap. In some examples of amorphous semiconductor components of the present invention, curves 39 and 40 of FIG. If it is not necessary to maintain the characteristics, it is not important. As previously mentioned, a wide range of designs for the structural arrangement and energy (band) gap E ₀₄ (eV) of the amorphous semiconductor component is possible, which can be provided by appropriate selection of the amorphous semiconductor material. be able to.
For example, the following amorphous semiconductor materials can have an energy gap of less than or equal to E ₀₄ .
That is, Si-1.5; SiC-2.06; B ₄ C-3.0; etc. These amorphous semiconductors can also be modified with modifying materials to provide extrinsic conduction and the desired activation energy E and electrical conductivity σ _RT at room temperature (and above). The combination of the elements of small atomic weight boron, carbon, nitrogen, oxygen with each other and with other elements results in a high melting temperature T _M (°C) and a correspondingly high crystal and glass transition temperature, and also a high bonding strength E _B
(eV), as mentioned above, provides an amorphous semiconductor member that can withstand high temperatures and has good strength properties, some examples of which are listed below.

[Table] Generally, when an element of low atomic weight is deposited in combination with other elements, the combination of elements has a higher melting point and higher bonding strength than the combination of other elements. An amorphous semiconductor component comprising an amorphous host matrix of amorphous semiconductor material and a modifying material added thereto, such as by co-sputtering, may, for example,
B ₄ C+W, BN+W, SiC+W, Si ₃ N ₄ +W, SiO ₂
+W, TeO ₂ +Ni, etc. The modified substance is
Substantially alters the electronic arrangement of the amorphous host matrix at room temperature and above. Energy gap (band gap) E ₀₄ (eV), electroactive energy E〓 (eV), electrical conductivity at room temperature σ _RT (Ω
The available documentation regarding physical and electrical activity, including the following: cm) ⁻¹ , Seebeck coefficient S (V/° C.) and p or n type is exemplified below. An additive material of an amorphous semiconductor material of boron and carbon (B ₄ C) and tungsten (W) which is intersputtered as described above and has the following properties.

[Table] The energy gap does not decrease, the active energy decreases substantially, the electrical conductivity increases substantially, the Seebeck coefficient changes substantially, and the conduction type remains P-type. . An additive-modified material of boron and nitrogen (BN) amorphous semiconductor material and tungsten (W) intersputtered as described above, having the following properties:

Table: The activation energy is substantially reduced and the electrical conductivity is substantially increased. An additive-modified material of silicon and carbon (SiC) amorphous semiconductor material and tungsten (W) intersputtered as described above, having the following properties:

[Table] The energy gap does not substantially decrease until a significant amount of tungsten is added, the electroactive energy does not substantially decrease until a significant amount of tungsten is added, and the electrical conductivity does not substantially decrease until a significant amount of tungsten is added. , the Seebeck coefficient changes substantially and the conduction type remains P type. An amorphous semiconductor material of silicon and nitrogen (Si ₃ N ₄ ) and tungsten (W) are intersputtered as described above and have the following characteristics:

Table: The electroactive energy is substantially reduced and the electrical conductivity is substantially increased. An additive-modified material of an amorphous semiconductor material of silicon and oxygen (SiO ₂ ) and tungsten (W), which is intersputtered as described above, having the following properties:

Table: The electroactive energy is substantially reduced and the electrical conductivity is substantially increased. An additive-modified material of an amorphous semiconductor material of tellurium and oxygen (TeO ₂ ) and nickel (Ni) having the following properties and intersputtered as described above.

[Table] The electroactive energy is relatively low, the electrical conductivity is relatively high, the Seebeck coefficient is relatively high,
The conduction type is P type. From the above examples, it can be seen that the amorphous semiconductor member of the present invention is
It can be easily designed to provide components with desired physical and electrical properties to manufacture many devices for a variety of applications. Substitutional doping can be applied to almost all nearest-neighbor fields.
This allows a tetrahedral-type local environment in the tetrahedral material by providing neighbor sites). This applies to both crystalline materials and glow discharge amorphous silicon. The present invention provides even more nearest neighbor joining choices. This is a normal result of amorphous nature. The large number of changing electron orbitals and bond relationships make the substitution of one atom in a regularly spaced matrix inappropriate. What you need is
The idea is to take into account the possibility of multiple bonds and exploit them through modification to control electrical conductivity. Boron is not the only good example of multiple electron orbitals in the amorphous phase; just as in organic materials, carbon atoms also provide multiple orbital interactions with other inorganic materials. Therefore, it is a non-primary bond that is an important feature of the invention. Not only the elements of groups 1 and 2 are important, but also the first row thereof, including boron and carbon, is important as a bonding matrix due to the different bonding possibilities they offer. By using first row elements including boron, carbon, nitrogen and/or oxygen, the amorphous semiconductor component can also withstand high temperatures and have good strength properties.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing one embodiment of the semiconductor device of the present invention, FIG. 2 is a diagram showing another embodiment of the semiconductor device of the present invention, and FIG. 3 is a diagram showing an amorphous semiconductor member of the present invention. A diagram of a p-n junction type device using
FIG. 4 shows a curve showing the absorption coefficient versus energy gap and illustrating the small difference between the energy gap of an unmodified amorphous semiconductor material and the energy gap of a modified amorphous semiconductor material; Figure 5 shows the electrical conductivity versus the reciprocal of temperature,
Figure 3 shows curves illustrating the activation energies of unmodified and modified amorphous semiconductor materials with various modifications. 10, 10A, 22... semiconductor device, 11...
Amorphous semiconductor member, 12...substrate, 13...amorphous semiconductor material, 14...change material, 16, 17...electrode.

Claims (1)

Claims: 1. Formed in a solid amorphous host matrix with a structural arrangement having local rather than long-range order, and an electronic configuration that provides an energy gap and electrical activation energy. an amorphous semiconductor material containing at least one element with a small atomic weight such as boron, carbon, nitrogen, or oxygen and consisting of a plurality of elements; and an element selected from the group consisting of nickel and tungsten; an amorphous semiconductor member comprising a modifying substance added to an amorphous host matrix, the modifying substance interacting with the electron orbits of the amorphous host matrix to cause, at a temperature above room temperature, An amorphous semiconductor component having electron trajectories that form electronic states in an energy gap that alter the electronic configuration of an amorphous host matrix so as to cause a change in electrical conductivity. 2. The amorphous semiconductor member of claim 1, wherein the amorphous semiconductor material of the amorphous host matrix contains at least two elements of the boron, carbon, nitrogen, or oxygen. 3. The amorphous semiconductor member of claim 2, wherein the amorphous semiconductor material of the amorphous host matrix contains boron and nitrogen. 4. The amorphous semiconductor member of claim 2, wherein the amorphous semiconductor material of the amorphous host matrix contains boron and carbon. 5. The amorphous semiconductor member of claim 1, wherein the amorphous semiconductor material of the amorphous host matrix contains silicon and nitrogen. 6. The amorphous semiconductor member of claim 1, wherein the amorphous semiconductor material of the amorphous host matrix contains silicon and oxygen. 7. The amorphous semiconductor member of claim 1, wherein the amorphous semiconductor material of the amorphous host matrix contains silicon and carbon. 8. The amorphous semiconductor member of claim 1, wherein the amorphous semiconductor material of the amorphous host matrix contains tellurium and oxygen. 9. Claims 1-8, wherein the amorphous host matrix is formed and the modifying material is added by co-sputtering the amorphous semiconductor material and the modifying material. The amorphous semiconductor member according to any one of the above. 10. Claim 1, wherein the modifying material added to the amorphous host matrix reduces its electrical activation energy and therefore increases the electrical conductivity of the semiconductor component at room temperature and above.
The amorphous semiconductor member according to any one of Items 1 to 9. 11. Claims 1 to 10, wherein the modifying substance added to the amorphous host matrix changes the Seebeck coefficient of the semiconductor component.
The amorphous semiconductor member according to any one of the items. 12. The amorphous semiconductor member according to any one of claims 1 to 11, which can withstand high temperatures and has good strength properties.