Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N99/00—Subject matter not provided for in other groups of this subclass
  • H10N99/05—Devices based on quantum mechanical effects, e.g. quantum interference devices or metal single-electron transistors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
  • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
  • H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
  • H01L29/26—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, elements provided for in two or more of the groups H01L29/16, H01L29/18, H01L29/20, H01L29/22, H01L29/24, e.g. alloys
  • H01L29/267—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, elements provided for in two or more of the groups H01L29/16, H01L29/18, H01L29/20, H01L29/22, H01L29/24, e.g. alloys in different semiconductor regions, e.g. heterojunctions
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
  • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
  • H01L29/86—Types of semiconductor device ; Multistep manufacturing processes therefor controllable only by variation of the electric current supplied, or only the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched
  • H01L29/861—Diodes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
  • H10N10/80—Constructional details
  • H10N10/85—Thermoelectric active materials
  • H10N10/851—Thermoelectric active materials comprising inorganic compositions
  • H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy

Definitions

• This invention relates to low-dimensional materials and, specifically, to low-dimensional materials which support a quantum self-thermalization and a quantum self-localization, as well as the quantum phase transition between said quantum phases, by means of a controlled variation in the quantum entanglement of carbon-like artificial nuclei in tetravalent artificial atoms that self- assemble.
• Clausius (1851) This paper is hereinafter referred to as Clausius (1851).
• the Carnot cycle represented by Clausius (1851) is shown in FIG.1 with a somewhat different symbolic representation.
• the Carnot cycle in FIG. 1 comprises four infinitesimal variations in the working substance: (l) isothermal expansion A ⁇ B; (2) adiabatic expansion B->C; (3) isothermal compression C- D; and (4) adiabatic compression D-)A.
• isothermal expansion A ⁇ B the working substance is expanded at a constant temperature by the extraction of latent heat ⁇ 3 ⁇ 4 ⁇ from the high- temperature T heat reservoir.
• adiabatic expansion B ⁇ C the working substance is adiabatically cooled from to T- dT without an external heat exchange.
• a Carnot heat engine operating in accordance with the Carnot cycle in FIG. 1 constitutes a thermomechanical motor in which the difference between a larger latent heat ⁇ 3 ⁇ 4 ⁇ extracted from the high-temperature T heat reservoir and a lesser latent heat - ⁇ iQc ⁇ D thereafter discharged into a low- temperature T- dT heat reservoir is converted into mechanical work.
• the change in entropy AS is generally given by:
• the Carnot cycle is reversible, such that the Carnot heat engine can operate either as a motor or a refrigerator. Under such a condition, the equality holds in Eq. (l) such that entropy is therefore conserved in the Carnot cycle.
• the Carnot cycle in FIG. 1 can also be represented in the manner portrayed in FIG. 2, wherein the intensive thermodynamic variable along the ordinate is temperature and the extensive thermodynamic variable along the abscissa is entropy S.
• the conservation of entropy in the Carnot cycle is deceptive in that the capability to perform work upon demand requires a spontaneity due to an irreversible process.
• thermodynamics For chemical reactions ideally in thermomechanical equilibrium with the surroundings, the second law of thermodynamics can be expressed by:
• thermodynamics manifests an increase in entropy in any energy transformation progressing upon its own accord.
• the spontaneity of most fuels is due to a decrease in enthalpy, such that Eq. (3) is more specifically:
• Kirchhoff (1860) stated his law of radiation as: "The ratio between the emissive and absorptive power is the same for all bodies at the same temperature.” Kirchhoff's radiation law can be expressed in terms of a spectral radiance K(v,T).
• Planck (1901) derived the entropy S of each Planckian resonator as:
• the infrared portion of the blackbody spectrum obeys the Rayleigh- Jeans blackbody radiation law derived from Planck's blackbody radiation law, per Eq. (17), for hv « kT.
• thermodynamic cycle exploits the quantum phase transition between quantum thermalization and quantum localization.
• a phonovoltaic cell can be produced that generates a flow of electric charge in response to an impressed electrical load.
• the phonovoltaic cell comprises a pair of conductors, preferably metallic electrodes with a solid semiconductive material between them that has two contiguous zones with different Seebeck coefficients.
• the flow of electric charge is believed to cause a decrease in the entropy of the ambient due to an uncompensated increase in the entropy of the phonovoltaic cell in response to the impressed electrical load.
• the phonovoltaic cell under thermal equilibrium extracts latent heat from the ambient and converts it directly into an electromotive force without using any outside agency, any moving parts, any depletable working substance, or any impinging radiation.
• the electromotive force is generated by a complementary Seebeck effect due to an uncompensated increase in the quantum transition entropy, at a constant temperature, of a phase transition between a quantum localization and a quantum thermalization of artificial nuclei that behave as mobile Planckian resonators.
• the first zone preferably comprises the chemical elements boron and hydrogen and the second zone preferably comprises the chemical elements boron, hydrogen and oxygen.
• the first zone is a boron layer comprising icosahedral boron and hydrogen and has a higher relative atomic concentration of boron than any other atom and the second zone is a boron layer comprising icosahedral boron, oxygen and hydrogen and has a higher relative atomic concentration of boron than any other atom.
• both the first and second zones also contain silicon. It is further preferred that each zone has a thickness of 4 nm or less.
• the first zone is a silaborane, preferably having a formula of (Bi 2 H w ) x Si y , wherein 3 ⁇ w ⁇ 5, 2 ⁇ x ⁇ 4, and 3 ⁇ y ⁇ 5 and the second zone is an oxysilaborane having a formula of (Bi 2 H w ) x Si y O z , wherein 3 ⁇ w ⁇ 5, 2 ⁇ x ⁇ 4, 3 ⁇ y ⁇ 5 and 0 ⁇ z ⁇ 3.
• p-isotype rectifiers are preferably in situ stacked in order to form a phonovoltaic pile comprising the phonovoltaic pile with the second conductor of a first phonovoltaic cell forming the first conductor for the next contiguous phonovoltaic cell.
• a p-isotype rectifier is produced such that the electrical conductivity is asymmetrical with respect to the polarity of an impressed electromotive force between the anode and cathode contact electrodes.
• the rectifier is produced from a solid semiconductor material having two contiguous zones, with each such zone contacted by a separate conductor.
• the two contiguous zones have different mobile-charge concentrations, such that the electrical conductivity is asymmetrical with respect to the polarity of an impressed electromotive force between the contact electrodes of said contiguous zones.
• An asymmetrical electrical conductance is considered to be a considerably greater current flow when one electrode is negatively biased relative to the other as compared to when the electrode is positively biased relative to the other.
• the first (anode) zone is a boron layer comprising icosahedral boron and hydrogen and has a higher relative atomic concentration of boron than any other atom
• the second (cathode) zone is a boron layer comprising icosahedral boron, oxygen and hydrogen and has a higher relative atomic concentration of boron than any other atom.
• both the first and second zones also contain silicon. It is also preferred that each zone has a thickness of 4 nm or less.
• the first zone is a silaborane, preferably having a formula of (Bi 2 H w ) x Si y , wherein 3 ⁇ w ⁇ 5, 2 ⁇ x ⁇ 4, and 3 ⁇ y ⁇ 5 and the second zone is an oxysilaborane having a formula of (Bi 2 H w ) x Si y O z , wherein 3 ⁇ w ⁇ 5, 2 ⁇ x ⁇ 4, 3 ⁇ y ⁇ 5 and 0 ⁇ z ⁇ 3.
• a conductor used in an integrated circuit can be formed where the effective resistance of the conductor is lower than that of a copper conductor having the same dimensions.
• the conductor is believed to displace electrical energy, in the absence of an electric field, without the actual displacement of electric charge. This is accomplished by using a solid semiconductor material whose electrical properties are modified by use of a trace amount of a metal, and in particular a coinage metal, to modify the electrical conductivity properties of the conductor. It is currently believed that this results in a microwave zitterschul Aharanov- Bohm effect that intrinsically generates a periodic driving force within the solid semiconductor material that is capable of displacing an electromagnetic power density through space without the aid of an outside agency.
• the conductor can connect two circuit elements, e.g. resistors, capacitors, diodes, power supplies, inductors, transformers, wires, or conductors, in an integrated circuit.
• the conductor can be used in the back end of line (BEOL) interconnects, including at sizes that are below 50 nm.
• BEOL back end of line
• the conductor comprises icosahedral boron, hydrogen and, optionally oxygen and has a higher relative atomic concentration of boron than any other atom.
• the conductor incorporates a trace amount of a coinage metal, such as gold, copper, and silver.
• a trace amount is an amount that is enough to alter the electrical conductivity of the conductor, which is believed to occur by partially or completely offsetting the nuclear electric quadrupole moment of the natural boron atoms, but not enough to affect the basic stoichiometric ratios of the conductor.
• the coinage metal is gold and it is preferably incorporated into the conductor at an atomic concentration of about 10 18 cm " 3.
• the conductor also contains silicon.
• the conductor is a silaborane, preferably having a formula of (Bi 2 H w ) x Si y , wherein 3 ⁇ w ⁇ 5, 2 ⁇ x ⁇ 4, and 3 ⁇ y ⁇ 5 or, to a lesser degree of preference, an oxysilaborane having a formula of (Bi 2 H w ) x Si y O z , wherein 3 ⁇ w ⁇ 5, 2 ⁇ x ⁇ 4, 3 ⁇ y ⁇ 5 and 0 ⁇ z ⁇ 3.
• FIG.1 is an illustration of the Carnot cycle
• FIG.2 is an another illustration of the Carnot cycle
• FIG. 3 is an illustration of Gibbs equilibration of a nonequilibrium state
• FIG.4 depicts a regular icosahedron inscribed in a cube in the manner employed by Longuet-Higgins and Roberts;
• FIG. 5 depicts the proposed nearly-symmetrical nuclear configuration of a boron icosahedron wherein the three-center bonds are described in terms of 24 delocalized tangential atomic orbitals 3 ⁇ 43 ⁇ 4(P ⁇ m ⁇ );
• FIG. 6 depicts an energy diagram showing the proposed energy levels of the clustered nuclei of the regular boron icosahedron shown in FIG. 5;
• FIG. 7 depicts an energy diagram showing the proposed energy levels of the clustered valence electrons of the regular boron icosahedron shown in FIG. 5;
• FIG.8 is an illustration of a regular boron icosahedron with a symmetrical nuclear configuration shown with four hydrogens bonded by a Debye force;
• FIG.9 is an illustration of a monocrystalline silicon unit cell
• FIG. 10 is an illustration of a diamond-like picocrystalline unit cell
• FIG. 11 is an energy level diagram depicting the occupied energy levels of the first eight valence electrons obeying Dirac's relativistic wave equation
• FIG. 12 is an energy level diagram depicting the occupied energy levels of the first twelve valence electrons obeying Dirac's relativistic wave equation
• FIG. 13 is an energy level diagram depicting the occupied energy levels of the first twenty-four valence electrons obeying Dirac's relativistic wave equation
• FIG. 14 is an energy level diagram depicting the occupied energy levels of the first thirty-two valence electrons obeying Dirac's relativistic wave equation
• FIG. 15 is an energy level diagram depicting the occupied energy levels of the thirty-six valence electrons obeying Dirac's relativistic wave equation
• FIG. 16 depicts an energy level diagram illustrating a proposed first disentanglement of the ⁇ S sp m ) energy level into the
• FIG. 17 depicts an energy level diagram illustrating a proposed second disentanglement of the
• FIGS. 18 A-B depict energy diagrams believed to reflect the occupied energy levels by valence electrons in negatively-ionized and positively-ionized picocrystalline artificial borane atoms B 12 H 4 and B 12 H 4 101, due to
• FIG. 19 is an illustration of a diamond-like picocrystalline unit cell with the incorporation of natural oxygen atoms
• FIG. 20 depicts an energy level diagram illustrating a proposed disentanglement of the I— 2 1/2 > energy level into the
• FIG. 21 depicts a phonovoltaic cell 400 comprising multiple pairs of contiguous picocrystalline silaborane ⁇ -( ⁇ ⁇ ⁇ ⁇ regions and picocrystalline
• FIG. 22 is an another illustration of the Carnot cycle
• FIG. 23 is an illustration of a proposed quantum thermodynamic cycle
• FIGS. 24 A-D depict energy diagrams illustrating the proposed occupied electronic energy levels of the artificial nuclei of the first- and second-nearest neighbor picocrystalline artificial borane atoms 101 of a pair of conjoined picocrystalline silaborane / ⁇ -(B 12 H4) 3 Si 5 and picocrystalline oxysilaborane p- (B 12 H 4 ) 2 Si 4 0 2 + regions 401 and 402;
• FIGS. 25 A-D depict a proposed spontaneous mobile charge diffusion;
• FIGS. 26 A-D further depict a proposed mobile charge diffusion
• FIGS. 27 A-D still further depict a proposed mobile charge diffusion
• FIGS. 28 A-D depict a proposed spectral induction of valence electrons from intraicosahedral bonding suborbitals into intraicosahedral antibonding suborbitals in a picocrystalline silaborane p-(B 12 H 4 ) 3 Si 5 region;
• FIGS. 29 A-D depict a proposed self-thermalization of valence electrons in a picocrystalline silaborane p-(B 12 H 4 ) 3 Si 5 region due to the nuclear electric quadrupole moment of the natural boron atoms;
• FIG. 30 depict a proposed disproportionation in a picocrystalline silaborane j9-(B 12 H 4 )gSi 5 region;
• FIG. 31 is an illustration of a proposed quantum thermodynamic cycle
• FIG. 32 is an illustration of the Earth's energy budget
• FIG. 33 is an illustration of the spectral radiance of a blackbody
• FIG. 34 is a micrograph obtain by high-resolution transmission microscopy (HRTEM) of a picocrystalline borane solid deposited on monocrystalline silicon;
• FIG. 35 is an HRTEM fast Fourier transform (FFT) image of the mono- crystalline silicon substrate
• FIG. 36 is an FFT image of the picocrystalline borane solid
• FIG. 37 is a graph in terms of interplanar lattice d-spacings of the HRTEM diffraction intensity of the monocrystalline substrate
• FIG. 38 is a graph in terms of interplanar lattice d-spacings of the HRTEM diffraction intensity of the picocrystalline borane solid;
• FIG. 39 is a conventional ⁇ -2 ⁇ x-ray diffraction (XRD) pattern of a self- assembled picocrystalline borane solid
• FIG. 40 is a grazing incidence x-ray diffraction (GIXRD) scan of the same self-assembled picocrystalline borane solid in FIG. 39;
• GIXRD grazing incidence x-ray diffraction
• FIG. 41 is a second grazing incidence x-ray diffraction (GIXRD) scan of the same self-assembled picocrystalline borane solid scanned in FIG. 39;
• GIXRD grazing incidence x-ray diffraction
• FIG. 42 is an illustration of a silaboride film deposited on a donor-doped region of a monocrystalline substrate
• FIG. 43 is a graph of a GIXRD scan of the picocrystalline silaboride solid of Example 1;
• FIG. 44 is an illustration of an oxysilaborane film deposited over a donor- doped silicon region in accordance with Example 2;
• FIG. 45 is a conventional ⁇ -2 ⁇ x-ray diffraction (XRD) pattern of the thin oxysilaborane solid of Example 2;
• FIG. 46 is a graph of a GIXRD scan of the oxysilaborane solid of Example 2.
• FIG. 47 is an illustration of a silaborane film deposited on an -type silicon substrate in accordance with Example 3.
• FIG. 48 is an x-ray photoelectron spectroscopy (XPS) depth profile of the silaborane film deposited in Example 3;
• FIG. 49 is an Auger electron spectroscopy (AES) depth profile of the silaborane film deposited in Example 3;
• FIG. 50 is an illustration of a silaborane film deposited on a >-type silicon substrate in accordance with Example 4.
• FIG. 51 is an x-ray photoelectron spectroscopy (XPS) depth profile of the silaborane film deposited in Example 4;
• FIG. 52 is a linear graph of the current-voltage characteristics of the silaborane film deposited in Example 4, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by a mercury probe;
• FIG. 53 is a log-log graph of the current- voltage characteristics of the silaborane film deposited in Example 4, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by a mercury probe;
• FIG. 54 is an illustration of an oxysilaborane film deposited on a >-type silicon substrate in accordance with Example 5;
• FIG. 55 is an x-ray photoelectron spectroscopy (XPS) depth profile of the oxysilaborane film deposited in Example 5;
• FIG. 56 is a linear graph of the current-voltage characteristics of the oxysilaborane film deposited in Example 5, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by a mercury probe;
• FIG. 57 is a log-log graph of the current- voltage characteristics of the oxysilaborane film deposited in Example 5, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by a mercury probe;
• FIG. 58 is an x-ray photoelectron spectroscopy (XPS) depth profile of another embodiment of an oxysilaborane film deposited per Example 6;
• XPS x-ray photoelectron spectroscopy
• FIG. 59 is a linear graph of the current-voltage characteristics of the oxysilaborane film characterized in Example 6, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by a mercury probe;
• FIG. 60 is a log-log graph of the current-voltage characteristics of the oxysilaborane film characterized in Example 6, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by a mercury probe;
• FIG. 61 is an x-ray photoelectron spectroscopy (XPS) depth profile of yet another embodiment of an oxysilaborane film deposited per Example 7;
• XPS x-ray photoelectron spectroscopy
• FIG. 62 is a linear graph of the current-voltage characteristics of the oxysilaborane film characterized in Example 7, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by a mercury probe;
• FIG. 63 is a log-log graph of the current-voltage characteristics of the oxysilaborane film characterized in Example 7, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by a mercury probe;
• FIG. 64 is an x-ray photoelectron spectroscopy (XPS) depth profile of still another embodiment of an oxysilaborane film deposited in Example 8;
• XPS x-ray photoelectron spectroscopy
• FIG. 65 is a linear graph of the current-voltage characteristics of the oxysilaborane film characterized in Example 8, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by a mercury probe;
• FIG. 66 is a log-log graph of the current-voltage characteristics of the oxysilaborane film characterized in Example 8, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by a mercury probe;
• FIG. 67 is an x-ray photoelectron spectroscopy (XPS) depth profile of yet still another embodiment of an oxysilaborane film deposited in Example 9;
• FIG. 68 is a linear graph of the current-voltage characteristics of the oxysilaborane film characterized in Example 9, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by a mercury probe;
• XPS x-ray photoelectron spectroscopy
• FIG. 69 is a log-log graph of the current-voltage characteristics of the oxysilaborane film characterized in Example 9, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by a mercury probe;
• FIG. 70 is an illustration of a / ⁇ -isotype electrochemical rectifier comprising oxysilaborane film produced in accordance with Example 10;
• FIG. 71 is a linear graph of the current-voltage characteristics of the p- isotype electrochemical rectifier in Example 10, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by microprobes;
• FIG. 72 is a linear graph of a different current-voltage range of the p- isotype electrochemical rectifier in Example 10, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by microprobes;
• FIG. 73 is a log-log graph of forward-bias current-voltage characteristics of the j9-isotype electrochemical rectifier in Example 10, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by microprobes;
• FIG. 74 is a log-log graph of reverse-bias current-voltage characteristics of the j9-isotype electrochemical rectifier in Example 10, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by microprobes;
• FIG. 75 is a linear graph of the current-voltage characteristics of the p- isotype electrochemical rectifier in Example 11, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by microprobes;
• FIG. 76 is a linear graph of a different current-voltage range of the p- isotype electrochemical rectifier in Example 11, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by microprobes;
• FIG. 77 is a log-log graph of forward-bias current-voltage characteristics of the j9-isotype electrochemical rectifier in Example 11, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by microprobes;
• FIG. 78 is a log-log graph of reverse-bias current-voltage characteristics of the j9-isotype electrochemical rectifier in Example 11, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by microprobes;
• FIG. 79 is a linear graph of a first current-voltage range of the / ⁇ -isotype electrochemical rectifier in Example 12, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by means of microprobes;
• FIG. 80 is a linear graph of a second current-voltage range of the / ⁇ -isotype electrochemical rectifier in Example 12, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by means of microprobes;
• FIG. 81 is a linear graph of a third current-voltage range of the / ⁇ -isotype electrochemical rectifier in Example 12, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by means of microprobes;
• FIG. 82 is a log-log graph of forward-bias current-voltage characteristics of the j9-isotype electrochemical rectifier in Example 12, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by microprobes;
• FIG. 83 is a log-log graph of reverse-bias current-voltage characteristics of the j9-isotype electrochemical rectifier in Example 12, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by microprobes;
• FIG. 84 is an illustration of an electrochemical device comprising a silaborane film produced in accordance with Example 13;
• FIG. 85 is a linear graph of the current-voltage characteristics of the electrochemical device in Example 13, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by microprobes;
• FIG. 86 is a linear graph of a second current-voltage characteristics of the electrochemical device in Example 13, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by microprobes;
• FIG. 87 is a log-log graph of forward-bias current-voltage characteristics of the electrochemical device in Example 13, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by microprobes
• FIG. 88 is a log-log graph of reverse-bias current-voltage characteristics of the electrochemical device in Example 13, as measured by an HP-4145 parameter analyzer with the sweep signals obtained by microprobes;
• FIG. 89 is an illustration of an oxysilaborane film deposited on a >-type silicon substrate in accordance with Example 14;
• FIG. 90 is an x-ray photoelectron spectroscopy (XPS) depth profile of the oxysilaborane film deposited in Example 14;
• FIG. 91 is an illustration of the thermal processing budget of the
• FIG. 92 is a geometric representation of an energy equilibration proposed by Josiah Willard Gibbs;
• FIG. 93 is a geometric representation of an entropy equilibration proposed by Josiah Willard Gibbs;
• FIGS. 94 A-B is an illustration comparing a phonovoltaic cell and a photovoltaic cell in the dark;
• FIGS. 95 A-B is an illustration comparing a phonovoltaic cell and a photovoltaic cell in which mobile electron-hole pairs are radiatively induced;
• FIGS. 96 A-B is an illustration comparing a phonovoltaic cell and a photovoltaic cell in which induced mobile electron-hole pairs are separated;
• FIGS. 97 A-B is an illustration comparing a phonovoltaic cell and a photovoltaic cell in which an electrical load is impressed;
• FIGS. 98 A-B is projected manufacturing cost analysis of a phonovoltaic cell
• FIGS. 99 A-B is an illustration comparing a phonovoltaic cell, a photovoltaic cell, and a thermionic converter
• FIG. 100 is an illustration of a device comprising an oxysilaborane film and gold produced in accordance with Example 15;
• FIG. 101 is an x-ray photoelectron spectroscopy (XPS) depth profile of the oxysilaborane film deposited in Example 15;
• XPS x-ray photoelectron spectroscopy
• FIG. 102 is secondary ion mass spectroscopy (SIMS) performed to measure a trace impurity concentration of gold in the oxysilaborane film in Example 15;
• SIMS secondary ion mass spectroscopy
• FIG. 103 depicts metal electrodes 536 and 537 evaporated over the gold film containing device of Example 15;
• FIG. 104 is a linear graph of the current-voltage characteristics of the oxysilaborane film in Example 15; DESCRIPTION OF THE PREFERRED EMBODIMENTS
• a regular icosahedron is inscribed in a cube in FIG. 4 such that the coordinates of the icosahedral vertices are described, subject to Eq. (21), in terms of the following position coordinates: ( ⁇ , ⁇ 1, 0), (0, ⁇ , ⁇ 1), and ( ⁇ 1, 0, ⁇ ).
• any orientation along, or parallel to, any cubic edge is generally represented by (100).
• Any particular (100) orientation e.g. the [010] orientation along the positive ⁇ y-axis, will be specifically denoted.
• a cubic face, or a plane parallel to a cubic face is generally represented by ⁇ 100 ⁇ .
• a particular ⁇ 100 ⁇ plane, e.g. the jcz-plane normal to the [010] direction, is represented by (010).
• a particular (100) orientation, e.g. the [010] orientation is always normal to the corresponding ⁇ 100 ⁇ plane, viz. the (010) plane in this case.
• any orientation along, or parallel to, a cubic body diagonal is represented by (111).
• icosahedral faces There are two classes of icosahedral faces: 8 icosahedral faces are constituted by ⁇ 111 ⁇ planes normal to a (111) cubic body diagonal and 12 icosahedral faces are constituted by ⁇ 00 _1 O ⁇ planes intersecting in pairs along a (100) orientation. Three-center bonds exist along edges of the ⁇ 111 ⁇ planes. [0047] In connection with the invention described here, a molecular orbital analysis, which describes the three-center boron bonds by a generalization of the methodology of Longuet-Higgins and Roberts performed in [0020] -[0063] of U. S. Provisional Application No. 62/591,848, is incorporated herein by reference.
• That generalized molecular orbital analysis describes a regular boron icosahedron 104 comprising 12 boron nuclei 102, with a nearly-symmetrical nuclear configuration, that is constituted by 24 delocalized atomic orbitals 3 ⁇ 43 ⁇ 4(P ⁇ m ⁇ ) i n a nearly-spherical spheroid wherein displacement is ideally limited to the 8 k ⁇ m ) wave vectors.
• the boron icosahedron 104 in FIG. 5 is referred to herein as an artificial nucleus 104.
• short-range periodic translational order is defined as a regular repetition of atomic positions over a space substantially confined to only first- and second-nearest neighbor atoms.
• the artificial nucleus 104 represented in FIG. 5 exhibits a short-range periodic translational order in which the 12 boron nuclei 102 ideally remain stationary at the 12 icosahedral vertices, such that all icosahedral displacement is ideally limited to only periodic vibrations along the 8 k ⁇ m > wave vectors.
• the artificial nucleus 104 in FIG. 5 constitutes a quantum Floquet-many-body subsystem that behaves similar to the nucleus of a natural carbon atom.
• a quantum Floquet-many-body system is a time-dependent many-body system that is periodic over time by virtue of its own dynamics.
• it is purposeful to establish the quantum entanglement of the atomic orbitals 3 ⁇ 43 ⁇ 4(P ⁇ m ⁇ ) forming the quantum Floquet-many-body subsystem of the artificial nucleus 104.
• the analysis of the artificial nucleus 104 in FIG. 5 was performed in terms of the group analysis of a regular icosahedron.
• the icosahedral symmetry group I h is unique amongst all the other symmetry groups in that it possesses the largest number of symmetry operations (120) of any symmetry group in Nature.
• the largest number of symmetry operations allowed in any crystallographic point group is 48, such that the icosahedral symmetry group I h is not a crystallographic point group that can support spatial crystals which exhibit a long-range periodic translational order.
• the inability of the icosahedral symmetry group I h to support a long-range periodic translational order allows it to, more generally, support an intrinsic spontaneous time-translational symmetry breaking to be described.
• the artificial nucleus 104 in FIG. 5 constitutes a manifestation of the quantum Floquet-many-body fermion system with the highest possible degree of symmetry in Nature.
• a fermion is a subatomic particle, subject to the Pauli exclusion principle, which is characterized by Fermi-Dirac statistics, as well as, any composite particle comprised of an odd number of said subatomic particles.
• a quantum Floquet-many-body system comprising fermions at the vertices of a regular icosahedron will be hereinafter referred to as an icosa- hedral Floquet-many-fermion system.
• the 12 boron nuclei 102 of the artificial nucleus 104 are initially assumed to be boron ⁇ B nuclei comprising an odd number of both protons and neutrons. An incorporation of the other natural boron isotope ⁇ B will be later considered hereinbelow.
• the icosahedral Floquet-many-fermion system of the particular artificial nucleus 104 in FIG. 5 possesses the highest degree of degree of symmetry in Nature relative to the icosahedral vertices at which the 12 boron nuclei 102 reside.
• the great circles associated with the quadrupole spherical harmonics contain the k ⁇ u l ) wave vectors of the artificial nucleus 104 in FIG. 5.
• the symmetry analysis of the artificial nucleus 104 in FIG. 5 is of a general nature, without any commitment as to the physical size of the icosahedral Floquet-many-fermion system.
• the distance between opposite icosahedral faces of the artificial nucleus 104 is ideally 269 pm, such that it is specifically referred to as an icosahedral Floquet-many-fermion picocrystal.
• the distance between the opposite icosahedral faces of the natural nucleus of carbon can be measured in
• nucleus 104 exhibits the same symmetry as the natural nucleus of carbon 6 C.
• Jahn-Teller effect results in a symmetry-breaking that lifts electronic orbital degeneracies by normal displacements of the 12 boron nuclei 102, known as Jahn-Teller-active modes, that distort polyatomic ions and molecules in the absence of spin-orbit coupling.
• Jahn and Teller intentionally ignored spin effects.
• Spin-orbit coupling is essential to preserving the intraicosahedral bonding of the icosahedral Floquet-many-fermion picocrystal of the artificial nucleus 104, subject to the intraicosahedral bonding and antibonding orbitals portrayed in FIG. 7.
• the quantum entanglement of the electronic eigenstates shown in FIG. 7 cannot exist in the presence of any Jahn-Teller distortion.
• quantum entanglement causes the icosahedral Floquet-many- fermion picocrystal comprising the artificial nucleus 104 to physically behave as a Planckian resonator that can be chemically modified in novel and useful ways by controlled variations in the quantum entanglement of the energy levels.
• Einstein formed this conclusion by a consideration of the relativistic translational Doppler shift of a radiative body. In extending his special theory of relativity to include rotation in his general theory of relativity, Einstein was unable to derive a relativistic rotational Doppler shift.
• a rotating fermion since a rotating fermion necessarily emits radiation, then a rotating fermion can only stabilize as a member of a quantum many-body system in which pairs of complementary rotational Doppler shifts stabilize said quantum many- body system.
• the icosahedral Floquet-many-fermion picocrystal of the artificial nucleus 104 constitutes a stabilized quantum many-body system of fermions that can be described by Dirac's relativistic wave equation. Dirac's energy eigenvalues for a Dirac many-body system of fermions obtained within [0086]-[0167] of U. S. Provisional Application No. 62/591,848 are incorporated herein by reference.
• a heretofore-unknown chemical fusion can be established by atoms chemically bonded together by the transformation of a small quantity of matter m into some energy E of a Dirac quasip article.
• a Dirac quasiparticle is a quantum Floquet-many-fermion system due to a dynamic interaction between fermions that entangles the individual energy levels.
• the second bound-energy term on the right side of Eq. (25 a) is due to the fine structure of a spinning fermion.
• the salient properties of a fermion fine structure are cogently described in order to better understand real-world devices comprising preferred embodiments of this invention.
• quantum chemistry involves a finite variation in the quantity of matter of the chemical reactants and products due to fusion.
• the role of quantum chemistry in this invention will be further discussed below.
• the concept of apeiron was initially conceived by Anaximander of Miletus circa 585 BC.
• the ability to exploit electric charge e in a quantum thermodynamic cycle, capable of replacing a Carnot cycle, can only be achieved when electric charge e is provided a mechanical basis.
• the mechanical basis of electric charge e is fundamentally derived in [0794]-[0846] of U. S. Provisional Application No. 62/591,848 and incorporated herein by reference.
• Wien's spectral displacement law supports the following spectral displacement (i.e., a shift in frequency) at the constant irradiance
• Spectral displacement is capable of quantum mechanically supporting a heat engine.
• Einstein's molar heat capacity in Eq. (20) can be simplified as follows for a low-frequency Planckian resonator frequency, such that hv « kT.
• a picocrystalline artificial borane atom 101 constitutes: (l) an artificial nucleus 104 formed by a boron icosahedron comprising 12 natural boron nuclei 102 with a nearly-symmetrical nuclear configuration and (2) 4 artificial valence electrons constituted by 4 natural hydrogen atoms with the hydrogen nuclei 103 bonded to a boron icosahedron such that the 4 hydrogen valence electrons are aligned along a k( in > wave vector.
• the picocrystalline artificial borane atom 101 comprises a boron icosahedron with 36 boron valence electrons occupying intraicosahedral molecular orbitals, such that intericosahedral chemical bonds are by the hydrogen valence electrons.
• An electric quadrupole moment along the k ⁇ m ) vectors causes an electric dipole moment in hydrogen atoms, such that the hydrogen nuclei 103 bond by a Debye force to the artificial nucleus 104.
• a chemical bonding of the picocrystalline artificial borane atoms 101 is explained by a self-selective atomic replacement in the monocrystalline silicon unit cell 200 in FIG. 9, which is comprised of 8 silicon vertex atoms 201, 6 silicon face-center atoms 202, as well as, 4 silicon basis atoms 203.
• the 4 basis atoms 203 reside along a (111) cubic body diagonal in a tetrahedral arrangement.
• the mono- crystalline silicon unit cell 200 is periodically translated over space so as to form a monocrystalline silicon lattice wherein the silicon vertex atoms 201 and the silicon face-center atoms 202 are covalently bonded to, and only to, the four silicon basis atoms 203 along a (111) crystal orientation.
• the resultant monocrystalline silicon lattice has a long-range periodic translational order in terms of cubic unit cells of -0.5431 nm along each edge, without any (100) chemical bonds.
• a diamond-like picocrystalline silaborane unit cell 300 is constructed by replacing each silicon vertex atom 201 within the monocrystalline silicon unit cell 200 with a borane molecule 101, as shown in FIG. 10.
• the 8 borane molecules 101 at the vertices of the silaborane unit cell 300 in FIG. 10 are shared amongst 8 picocrystalline silaborane unit cells 300 in an extended solid lattice (not shown).
• the periodic translation of the picocrystalline silaborane unit cell 300 over space would, thereby, result in a picocrystalline silaborane (B 12 H 4 ) Si 7 solid lattice that effectively acts as a self-assembled diamond-like picocrystalline lattice structurally similar to monocrystalline silicon.
• the picocrystalline oxysilaboranes of this invention constitute nearly transparent solids that are believed to be formed by a continuous random network of polyatomic unit cells obeying a modification of rules developed by Zachariasen in a paper "The Atomic Arrangement in Glass," Journal of the American Chemical Society, Vol. 54, 1932, pp. 3841-3851. All references hereinafter to Zachariasen are understood as referring to this paper. Zachariasen focused on oxide glasses and, more particularly, on amorphous S1O 2 and amorphous B2O3. Zachariasen proved that amorphous S1O 2 is constituted by a continuous random network of S1O 4 tetra- hedra.
• picocrystalline oxysilaboranes are believed to be constituted by the continuous random network of polyhedra with a nearly-symmetrical boron icosahedron at each of the eight polyhedra corners.
• picocrystalline oxysilaboranes constitute solids formed by the continuous random network of borane hexahedra which, by definition, are constituted by hexahedra with picocrystalline artificial borane atoms 101 at the hexahedral corners.
• FIG. 9 is a regular hexahedron (cube), the diamond-like picocrystalline silaborane unit cell 300 in FIG. 10, while portrayed for description purposes as a cube, is in actuality an irregular hexahedron.
• Zachariasen represented the atomic arrangement of an oxide glass by the continuous random network of polymorphic oxygen tetrahedra or triangles
• the atomic arrangement in a borane solid is described by a random network of irregular hexahedra.
• the eight corners of the borane hexahedron 300 in FIG. 10 are comprised of picocrystalline artificial borane atoms 101.
• Each corner picocrystalline artificial borane atom 101 is, ideally, bonded to four tetravalent natural atoms 303 which are surrounded by eight corner picocrystalline artificial borane atoms 101.
• the preferred tetravalent natural atoms 303 are natural silicon atoms.
• Each of the tetravalent natural atoms 303 bonds to one or more face-center atom 302 in the borane hexahedron 300 shown in FIG. 10.
• Each face-center atom 302 can be any of, but not limited to: a tetravalent natural atom such as silicon; a hexavalent natural atom such as oxygen; or, possibly, a tetravalent picocrystalline artificial borane atom 101.
• a tetravalent natural atom such as silicon
• a hexavalent natural atom such as oxygen
• a tetravalent picocrystalline artificial borane atom 101 With the help of the irregular borane hexahedron 300 shown in FIG. 10, the atomic arrangement of a borane solid can be understood.
• four tetravalent natural atoms 303 are surrounded by 8 corner picocrystalline artificial borane atoms 101 in a solid borane lattice.
• the conjoined irregular borane hexahedra 300 share common corner picocrystalline artificial borane atoms 101 within the continuous random network.
• centroid of the corner picocrystalline artificial borane atoms 101 is, ideally, motion-invariant.
• each corner picocrystalline artificial borane atom 101 covalently bonds to four tetravalent natural atoms 303 along a (111) crystalline orientation. It is noteworthy to recognize that the tetravalent natural atoms 303 are in the positions of the silicon basis atoms 203 (as shown in FIG. 9 in the unit cell of monocrystalline silicon) that undergo a spatial displacement to preserve the unit cell dimension.
• each irregular borane hexahedron 300 forming a solid lattice is ideally constituted by 8 corner picocrystalline artificial borane atoms 101, 6 face-center picocrystalline artificial borane atoms 101, and 4 natural silicon atoms 303.
• picocrystalline silaborane (B 12 H4) 4 Si4 forms a picocrystalline polymorph, similar to monocrystalline silicon, comprised of tetravalent natural silicon atoms 303 and tetravalent picocrystalline artificial borane atoms 101. It is by means of this type of structure that spin-orbit coupling becomes physically important. [0092] Preferred embodiments of this invention involve a type of order not known in the prior art.
• Long-range periodic translational order is defined herein as the regular repetition of a certain invariant arrangement of atoms, known as a unit cell, through space so as to thereby form a translationally-invariant tiling in a regular array of natural atoms well beyond first- and second-nearest neighbor natural atoms.
• Monocrystalline and polycrystalline materials exhibit a long-range periodic translational order throughout space. The periodic repetition of atomic positions is preserved throughout the entire space of a monocrystalline material. In a polycrystalline material, the periodic repetition of atomic positions is maintained over the limited finite space in grains, which can be themselves arbitrarily oriented over space.
• a nanocrystalline material is any polycrystalline material in which the grain sizes range between 300 pm and 300 nm.
• Short-range periodic translational order is defined hereinafter as the repetition of natural atomic positions over a space substantially confined to only the first- and second-nearest neighbor natural atoms.
• the radii of isolated neutral atoms range between 30 and 300 pm.
• any pico- crystalline material is a material exhibiting a short-range periodic translational order confined to repeating atomic positions in finite groups of first- and second- nearest neighbor natural atoms.
• An amorphous material as used hereinafter, is a material void of regularly repeating arrangements of atoms, so as to thus be incapable of supporting a constructive interference of x-rays.
• a "picocrystalline artificial atom” is a cluster, of a size less than 300 pm, of natural atoms that are mutually bonded together so as to support a short-range periodic translational order and an internal discrete quantization of energy levels.
• special types of picocrystalline artificial atoms can be bonded to other natural atoms in order to form an extended lattice of natural atoms and picocrystalline artificial atoms.
• a natural atom is any isotope of a stable chemical element contained in the periodic chart.
• a special type of picocrystalline artificial atom comprises a boron icosahedron with a nearly-symmetrical nuclear configuration.
• the singular material most responsible for the solid-state electronic revolution over the past six decades is monocrystalline silicon.
• monocrystalline silicon As the scaling of feature sizes of monolithic integrated circuits approaches molecular dimensions, the displacement of electric charge in extended energy bands over space increasingly breaks down due to fundamental quantum conditions. In a related manner, electric charge conduction in extended energy bands in low-dimensional metallic interconnects further degrades the performance of monolithic integrated circuits.
• monolayer graphene presents a challenge to an incorporation into monolithic integrated circuits due to the absence of a bandgap energy and an incompatible deposition process with integrated circuits.
• Preferred embodiments of this invention remedy scaling limitations of monolithic integrated circuits by a material amalgamation of monocrystalline silicon and graphene that supports a displacement of electrical action over space.
• picocrystalline artificial borane atoms 101 replace the silicon vertex atoms 201 in FIG. 10.
• picocrystalline silaborane ⁇ the six face-center atoms 302 are (although not shown in FIG. 10) picocrystalline artificial borane atoms 101.
• picocrystalline silaborane (B 12 H4) 4 Si4 does not possess any long- range periodic translational order in the manner of monocrystalline silicon. [0098] Due to the absence of a long-range periodic translational order, picocrystalline silaborane (B 12 H 4 ) 4 Si4 cannot physically support extended conduction and valence energy bands over space. The existence of van der Waals forces (and more particularly Debye forces) between picocrystalline artificial borane atoms 101 further eliminates extended conduction and valence energy bands over space in picocrystalline silaborane (B 12 H 4 ) 4 Si4.
• the quantum temperature ⁇ ⁇ of the continuous thermal resonator is much greater than the ambient temperature T. Since the artificial nuclei 104 forming picocrystalline silaborane (B 12 H 4 ) 4 Si 4 constitute open icosahedral Floquet-many-fermion picocrystals, then the quantum temperature ⁇ ⁇ of any artificial nucleus 104 is clamped at the ambient temperature T.
• FIG. 11 Per FIG. 11 four electrons initially occupy the +2p ⁇ /2 antibonding suborbital and four electrons initially occupy the -2p ⁇ /2 bonding suborbital of a Dirac quasip article.
• Two consequences of FIG. 11 distinguish Dirac quasip articles from fermions obeying Schrodinger's nonrelativistic wave equation.
• spectral induction is not known in the prior art, it is used in the successful operation of preferred embodiments of the present invention.
• the bound-energy eigenstates of a Dirac quasiparticle are involved in the chemical fusion of boron icosahedra comprising preferred embodiments of this invention.
• the spectral quantum number ⁇ of the electron fine structure is polarized - except for the highest bound-energy eigenstate in a shell.
• the occupancy of the ⁇ ⁇ 2p 3/2 ) eigenstates, along with the vacancy of the ⁇ ⁇ 2 sp° l/2 ) eigenstates, in FIG. 11 is due to the fact that the Gibbs free energy of the ⁇ ⁇ 2p s/2 ) eigenstates is lower than the Gibbs free energy of the
• a principal attribute of the artificial nucleus 104 comprising the picocrys- talline oxysilaboranes of this invention is the existence of excited eigenstates of a lower Gibbs free energy than that of the ground eigenstate in each shell.
• the stable unfilled shell condition in FIG.11 is due to a spontaneous excitation of valence electrons into the higher-angular-momentum suborbital of a doublet generated by spin-orbit coupling.
• This spontaneous excitation of electrons is due to a decrease in Gibbs free energy in the higher-angular-momentum eigen- states ⁇ +2p s/2 ) relative to the lower-angular-momentum eigenstates
• the n ⁇ 2 shells are completely closed if valence electrons fill the ⁇ 2sp 2 m ) eigenstates in FIG.12.
• +3s 1/2 ) eigenstate is positive, such that electrons are elevated by spin-orbit coupling.
• +3d 5/2 » > 0 in Eq. (45 a) causes electrons to occupy the
• a Dirac quasiparticle physically constituted by a boron icosahedron, with a nearly-symmetrical nuclear configuration is a quantum many-body system that is ideally closed to its surroundings due to entangled intraicosahedral anti- bonding and bonding orbitals occupied by valence electrons in the manner shown in FIG.15.
• a boron icosahedron, with a nearly-symmetrical nuclear configuration can be transformed into a semi-open quantum many-body system able to interact with its surroundings due to the boron nuclei.
• An oblate spheroidal nucleus exhibits a negative electric quadrupole moment and, conversely, a prolate spheroidal nucleus exhibits a positive electric quadrupole moment.
• boron constitutes the stable nuclide exhibiting the largest nuclear electric quadrupole moment per nucleon, due to a deformed nucleus.
• Boron 5 B has a nuclear angular momentum 33 ⁇ 4 and a large positive nuclear electric quadrupole moment of +0.085 x l0 ⁇ 28 e-m 2 whereas boron has a nuclear angular momentum 3/2% and, also, a nuclear electric quadrupole moment of +0.041 x l0 ⁇ 28 e-m 2 .
• the energy associated with the nuclear electric quadrupole moment of the boron nuclei is expressed as follows with the aid of Gauss' law.
• the energy associated with the nuclear electric quadrupole moment Q B) of boron relates to the boron concentration n(B) in picocrystalline silaborane. Assuming for present purposes that the principal boron isotopes ⁇ B and ⁇ B are in a naturally-occurring ratio, the nuclear electric quadrupole moment of boron is:
• the total energy EQ(B) 17.9 ⁇ + 31.3 ⁇ released by a disentanglement of the bonding I—3 s 1/2 > and ⁇ Spd s/2 ) eigenstates, due to the nuclear electric quadrupole moment of boron, was previously given hereinabove by the tico* column in Table 2.
• the quantum temperature ⁇ ⁇ is clamped at the ambient temperature T 0 , a small concentration 2p Q of the host picocrystalline artificial borane atoms 101 are self-thermalized.
• a self-thermalization of picocrystalline artificial borane atoms 101, per FIG. 17, causes picocrystalline silaborane (B 12 H4) 4 Si 4 to essentially behave as a j9-type semiconductor. This is due to the fact that the local disentanglement of the
• picocrystalline silaborane (B 12 H4) 4 Si 4 undergoes a disproportionation that causes an ionization of the partially-disentangled picocrystalline artificial borane atoms 101 into pairs of dianions and dications.
• >-type picocrystalline silaborane is better chemically represented as j9-(B 12 H ) 3 Si 5 .
• a 2 is the square of the fine structure constant - which provides an approximate magnitude of a trace disproportionation of dianion-dication pairs in / ⁇ -type picocrystalline silaborane j9-(B 12 H ) 3 Si 5 . It thus follows that >-type picocrystalline silaborane j9-(B 12 H ) 3 Si 5 is a semi-open mixed quantum many-body system comprising ⁇ 10 18 cm ⁇ 3 ionized
• An ionization of the artificial nuclei 104 of stationary picocrystalline artificial borane atoms 101 provides for a charge displacement by means of free charge trapped in various artificial nuclei 104.
• the total concentration of neutral picocrystalline artificial borane atoms 101 B 12 H is ⁇ 10 22 cm -3 while a much smaller trace concentration of the ionized picocrystalline artificial borane atoms 101 B 12 H and B 12 H is ⁇ 10 cm -3 . It is to be understood that an ionization of two neutral picocrystalline artificial borane atoms 101 B 12 H
• Electric charge can become self-trapped within an induced potential well, so as to be displaced through space with the self-trapped potential well as a quasip article.
• This type of quasip article is referred to as a polaron.
• the pair of trapped charges in a bipolaron can generally be either a pair of electrons or a pair of holes. Boron- rich solids are particularly well suited for bipolaron formation due to the strong
• a pair of holes of opposite spin can be self-trapped in a softening singlet bipolaron by symmetry-breaking vibrations in a specific vibronic (i.e., vibrational and electronic) eigenstate.
• These two types of singlet bipolarons exhibit different physical properties.
• the self-trapped hole-pair in a singlet Jahn-Teller bipolaron can be excited from the ground eigenstate by a photo-absorption
• a self- trapped hole-pair in a singlet softening bipolaron cannot be similarly excited.
• the hole-pairs remain self-trapped in singlet softening bipolarons, with a stabilization occurring by a lowering of the free energy of atomic vibrations of the lattice.
• the carrier-induced formation of singlet softening bipolarons contributes to an increase in the Seebeck coefficient due to the softening of symmetry-breaking lattice vibrations.
• Another enhancement of the Seebeck coefficient within boron carbide ⁇ i2+x ⁇ 3-x over the compositional range 0.15 ⁇ x ⁇ 1.7 can be related to a change in entropy due to a hopping of softening bipolaronic holes.
• the contributions to the Seebeck coefficient by a carrier-induced softening of the lattice vibrations and by the hopping of singlet softening bipolaronic hole-pairs are largely insensitive to a compositional variation. There exists a variation in the Seebeck coefficient over a compositional range of boron carbide B ⁇ + ⁇ C ⁇ . ⁇ due, in part, to disproportionation.
• Disproportionation is an irreversible non-cyclic process in which the entropy of mixing is maximized per the second law of thermodynamics.
• the fraction of ionized borane molecules that are ionized into borane dications is designated by c.
• the entropy of mixing associated with mobile ions can generally be described by the following relation.
• Natural oxygen atoms 304 occupy the six face-center atoms in the unit cell per FIG. 19.
• Picocrystalline silaborane / ⁇ -(B 12 H ) 3 Si 5 is thereby said to possess a
• the phonovoltaic cell 400 in FIG. 21 is constituted by multiple conjoined pairs of picocrystalline silaborane / ⁇ -(B 12 H ) 3 Si 5 regions 401 and thin picocrystalline oxysilaborane j9-(B 12 H ) 2 Si 0 2 + regions 402 intervened by the metallic electrodes 403. It is to be understood that the phonovoltaic cell 400 is, generally, constituted by any number of such pairs of conjoined regions 401 and 402 intervened by metallic electrodes 403.
• silaborane j9-(B 12 H ) 2 Si 0 2 regions constitute, respectively, the anode region 401 and the cathode region 402 of a / ⁇ -isotype rectifier 404.
• a phonovoltaic cell 400 is comprised of a number of j9-isotype rectifiers 404 intervened by metal electrodes 403, with aluminum being the preferred metal.
• silaborane j9-(B 12 H ) 2 Si 0 2 region 402 is substantially void of mobile holes
• the conjoined picocrystalline silaborane j9-(B 12 H ) 3 Si 5 anode region 401 at room temperature contains mobile holes at the trace concentration of ⁇ 10 18 cm -3 .
• Mobile holes therefore diffuse upon their own accord from the picocrystalline silaborane j9-(B 12 H ) 3 Si 5 anode region 401 into the conjoined picocrystalline oxysilaborane
• the occupied energy levels of the boron icosahedra that comprise picocrystalline silaborane / ⁇ -(B 12 H 4 ) 3 Si 5 are, ideally, represented in FIGS. 18A-B.
• the occupied energy levels of the boron icosahedra that comprise picocrystalline oxysilaborane j9-(B 12 H 4 ) 2 Si 4 0 2 + are, ideally, further represented within FIG. 20.
• the conjoined regions 401 and 402 in the phonovoltaic cell 400 support the diffusion of bipolaronic hole-pairs from each picocrystalline silaborane / ⁇ -(B 12 H ) 3 Si 5 region 401 into the conjoined picocrystalline oxysilaborane j9-(B 12 H ) 2 Si 4 0 2 + region 402.
• Bipolaronic hole-pairs diffuse on their own accord from the ⁇ -3p° 1/2 ) eigenstate of a picocrystalline silaborane / ⁇ -(B 12 H ) 3 Si 5 region 401 into the ⁇ -2p° 1/2 ) eigenstate of the conjoined picocrystalline oxysilaborane / 2— 2+
• a mixing of mobile holes between the anode and cathode regions 401 and 402 of each p- isotype rectifier 404 is due to conjoined regions of different compositions.
• the mixing of the mobile holes between the anode region 401 and the cathode region 402 is an irreversible process that proceeds on its own accord until the entropy of mixing S m i x is maximized. This process can be continuously sustained in the phonovoltaic cell 400 shown in FIG.
• the power stroke of the Carnot cycle within FIG. 22 is the adiabatic expansion A ⁇ B of the ideal gas working substance under spontaneous cooling.
• the ideal gas working substance is spontaneously cooled from the elevated temperature T 0 + dT until it is clamped at the lower ambient temperature T 0 .
• Thermomechanical work is performed by the working substance during adiabatic expansion A-)B.
• the power stroke of the quantum thermodynamic cycle in FIG. 23 is the adiabatic mixing A- B of the mobile-hole working substance under spontaneous cooling.
• the Seebeck coefficient a m i x due to a change in the entropy of mixing S m i x ranges from zero for B 13 C 2 to 105 ⁇ 7 ⁇ for B 12 15C2 35 over the compositional range 0.15 ⁇ x ⁇ 1.7 of single-phase boron carbide ⁇ i2 +x ⁇ 3- x -
• the generation of an electromotive force by the phonovoltaic cell 400 shown in FIG. 21 is due to a difference in the Seebeck coefficients of conjoined regions, it is impossible for this to be realized by conjoined compositions of boron carbide.
• the bipolaronic electron-hole concentration in the picocrystalline silaborane j9-(B 12 H 4 ) 3 Si5 anode region 401 at B remains p Q while the temperature is decreased during adiabatic mixing A ⁇ B from T 0 at A to T 0 - dT at B in FIG. 23.
• Clausius (1865) introduced the word "entropy” as the transliteration of the Greek word ⁇ that means “a turning towards.” [0145] Although not explicitly employed as such by Clausius (1865), a path- independent exact infinitesimal variation is denoted herein by d while any path- dependent inexact infinitesimal variation is denoted herein by d. The distinction between these two infinitesimal variations bears on the general statement of the second law of thermodynamics. Equation (2) in Clausius (1865) is expressed as:
• Clausius (1865) denoted the numerator of the integrand as dQ - even though he recognized the integrand as being path- dependent.
• the direction of the inequality in Eq. (l) is due to the fact that dQ is defined to be the path-dependent infinitesimal heat extracted by the working substance.
• the inequality is reversed if dQ is defined in terms of heat emitted by the working substance.
• Clausius (1865) denotes irreversibility: "Here the equality sign is to be used when all the changes making up the cyclic process are reversible.
• FIGS. 24 A-B The intraicosahedral electron energy conditions within the conjoined picocrystalline silaborane / ⁇ -(B 12 H 4 ) 3 Si 5 anode region 401 in the phonovoltaic cell 400 at the initial state A in FIG. 23 are shown in FIGS. 24 A-B.
• a bipolaronic hole- pair 2e + in the ionized artificial nucleus 104 is due to the missing electron-pair in the ⁇ -3p° 1/2 ) eigenstate shown in FIG. 24 B.
• disproportionation results in a trace concentration of ⁇ 10 18 cm -3 bipolaronic electron-hole pairs distributed amongst the ⁇ 10 22 cm -3 neutral artificial nuclei 104 comprising the picocrystalline silaborane / ⁇ -(B 12 H 4 ) 3 Si 5 anode region 401 of each / ⁇ -isotype rectifier 404 of the phonovoltaic cell 400.
• no bipolaronic holes ideally exist in the pico-
• silaborane j9-(B 12 H 4 ) 2 Si 4 C ) 2 cathode region 402 are then collected by the metallic electrode 403 contacting said cathode region 402.
• mobile bipolaronic electron-pairs 2e ⁇ hopping in the picocrystalline silaborane j9-(B 12 H 4 ) 3 Si 5 anode regions 401 are collected by the metallic electrodes 403 contacting said anode regions 401.
• the conclusion of adiabatic mixing A ⁇ B in FIG. 23 is represented, in part, by the electron energy levels of the phonovoltaic cell 400 shown in FIGS. 27A-D.
• the displaced bipolaronic electron-hole pairs under adiabatic mixing A ⁇ B are ionized mobile Planckian resonators comprising a pair of charges 2e ⁇ or 2e + and a vibrational energy S kT 0 (since hv « kT 0 ). In this manner, the energy of each mobile charge collected by the electrodes 403 is 3/2 kT 0 per the equipartition theorem.
• the loss of heat energy during adiabatic mixing A ⁇ B causes a decrease in temperature from T 0 at A to T 0 - dT at B in FIG. 23.
• This decrease in temperature perturbs the extrinsic concentration of the ionized artificial nuclei 104 in the picocrystalline silaborane p-(B 12 H4) 3 Si 5 anode regions 401 of / ⁇ -isotype rectifiers 404 comprising the phonovoltaic cell 400. Since the nuclear electric quadrupole moments of the stationary natural boron nuclei 102 remain unchanged, the left side of Eq. (50) remains invariant. As the result, the decrease in temperature due to adiabatic mixing A ⁇ B manifests a localization of bipolaronic hole-pairs.
• quantum thermodynamics differs from classical thermodynamics in a fundamental way.
• entanglement fundamentally distinguishes quantum mechanics from classical mechanics.
• the icosahedral symmetry operations maximize the entanglement of the atomic orbitals 3 ⁇ 43 ⁇ 4(P ⁇ m ⁇ ) so as to result in intraicosahedral antibonding and bonding electron energy levels obeying Dirac's relativistic energy eigenvalues in Eqs. (23 a-b).
• the electronic orbital degeneracies of the artificial nuclei 104 are lifted by a spin-orbit coupling in lieu of a Jahn-Teller distortion. It is by this means that the picocrystalline oxysilaboranes of the present invention are distinguished from all other icosahedral boron-rich solids. That is to say, the icosahedral symmetry is broken by Jahn-Teller distortion in all known icosahedral boron-rich solids in the prior art.
• any lowering of the temperature of picocrystalline silaborane p-(B 12 H4) 3 Si 5 necessarily results in an increase in the entropy of entanglement S ent such that electrons are excited from the condition in FIG. 27 B into the condition shown in FIG. 28 B by an extraction of latent heat.
• the increase in the entropy of entanglement S ent exactly compensates the decrease in the entropy of transition Si rans .
• the extracted latent heat in the isothermal phase transition B ⁇ C is physically transformed into stored electrical energy by virtue of the excitation of valence electrons in FIG. 28 B. The physical means by which this is accomplished will be described hereinbelow.
• FIG. 29 B Said self-thermalization is shown in FIG. 29 B.
• the self-thermalized neutral artificial nuclei 104 undergo an ionized disproportionation in the manner represented in FIGS. 30A-B.
• the resultant bipolaronic hole-pair concentration p >p 0 remains localized during the adiabatic self-thermalization C ⁇ D per FIG. 23.
• an isothermal phase transition D ⁇ A causes a decrease in the bipolaronic hole-pair concentration p within the picocrystalline silaborane j9-(B 12 H 4 ) 3 Si 5 anode regions 401 in the phonovoltaic cell 400 in accordance with:
• the isothermal phase transition D ⁇ A in FIG. 23 is associated with an uncompensated increase in the entropy of transition S trans from the localized state at D to the original thermalized state at A in FIG. 23 per FIGS. 24A-B.
• the isothermal phase transition D ⁇ A constitutes an uncompensated increase in the entropy of transition S trans , since the entropy of entanglement S ent of the artificial nuclei 104 can never decrease on its own accord.
• the decrease in the entropy of entanglement S ent associated with a disentanglement of intraicosahedral energy levels is due to the nuclear electric quadrupole moments of the boron nuclei 102 during the adiabatic self-thermalization C ⁇ D represented in FIG. 23.
• the isothermal phase transition D ⁇ A necessarily extracts the latent heat T 0 S trans from the ambient.
• the extraction of latent heat T 0 dS trans during the isothermal phase transition D ⁇ A of the phonovoltaic cell 400 constitutes the entropy equilibration originally conceived, but never physically implemented, by Gibbs (1873).
• the extracted latent heat T 0 dS trans from the ambient is directly transformed into a decrease in Gibbs free energy of mixing ⁇ dG m i x during A ⁇ B.
• the quantum thermodynamic cycle in FIG. 23 is modified in FIG. 31 in order to describe the phonovoltaic cell 400 in FIG. 21.
• the reversible Carnot cycle in FIG. 22 transforms the net consumed latent heat dQ ⁇ , ⁇ A ⁇ ⁇ 3 ⁇ 4?B ⁇ C into thermomechanical work - dW associated with the adiabatic expansion A ⁇ B of an ideal gas working substance
• the irreversible quantum thermodynamic cycle per FIG. 31 transforms the extracted latent heat eT 0 da tra ns into an electromotive force eVout associated with the adiabatic mixing A ⁇ B of a unique electric charge working substance. It is extremely important that:
• the output voltage V ou t of the phonovoltaic cell 400 in FIG. 21 is due to the isothermal extraction of latent heat eT 0 da trans from the ambient without the need for a second heat reservoir.
• the phonovoltaic cell 400 in FIG. 21 is an irreversible thermoelectric engine operating in thermal equilibrium with the ambient heat reservoir, without the requirement of a second heat reservoir at a different temperature.
• the phonovoltaic cell 400 in FIG. 21 remedies fundamental limitations of all heat engines in the prior art.
• the phonovoltaic cell 400 eliminates the need to generate a high-temperature heat reservoir by means of combustion or any other process using a depletable energy source.
• the energy source of the phonovoltaic cell 400 in FIG. 21 is latent entropy in the biosphere.
• thermoelectric work eV out delivered by the phonovoltaic cell 400 to an electrical load is directly transformed from an entropy reduction of the ambient, as originally conceived by Gibbs (1873), such that there is no net entropy change in the biosphere by virtue of the performance of work upon demand. That is to say, the entropy decrease of the biosphere due to the operation of the phonovoltaic cell 400 is compensated by the entropy increase of the biosphere associated with the work done upon demand by an impressed electrical load.
• the profound novelty and utility of the embodiments of this present invention can be framed in terms of the Earth's energy budget in FIG. 32, which was prepared by NASA by means of actual data averaged over a ten year period.
• the solar radiation impinging upon Earth's atmosphere is emitted from the Sun's photosphere, which is at an effective temperature of 5,777 °K that corresponds to a radiation frequency of 120 THz.
• the infrared radiation emitted by the Earth at 300 °K is at a frequency of 6.2 THz.
• the irradiance of the back radiation from the atmosphere in FIG. 32 is 340 W/m 2 (or, also, 34 mW/cm 2 ).
• the Earth's energy budget can be framed by means of Planck's blackbody radiation law in Eq. (16).
• Planck's blackbody radiation law in Eq. (16) completely describes the spectral radiance emitted by a blackbody radiator in thermal equilibrium at any given temperature.
• a plot of various spectral radiance curves subject to Planck's blackbody radiation law for various radiator temperatures is provided in FIG. 33.
• the integral of each spectral radiance curve over all wavelengths and the entire solid angle results in the power flux density
• the irradiance of blackbody radiation is a function of only the radiator temperature.
• 34 mW/cm 2 .
• Wien's spectral displacement law provides for work being done on, or by, radiation at a constant irradiance
• 34 mW/cm 2 that corresponds to the radiator temperature.
• the 120 THz solar radiation impinging upon the Earth's surface and the 6.2 THz terrestrial radiation emitted by Earth's surface occur at a constant irradiance
• 34 mW/cm 2 per Eq. (64).
• the energy of a photon at 120 THz is 0.50 eV while the energy of a photon at 6.2 THz is 25.9 meV.
• the energy budget of Earth's biosphere can be viewed as the energy difference between the incoming solar radiation and the outgoing terrestrial radiation at a constant irradiance
• 34 mW/cm 2 .
• thermomechanical engines necessarily limited in efficiency by the Carnot cycle, discharges latent heat into the biosphere, so as to thereby increase the entropy of the biosphere.
• the Carnot heat engine is the only reversible thermomechanical engine that operates between two heat reservoirs at different temperatures. All other thermomechanical engines are irreversible heat engines with a lower efficiency than the Carnot heat engine.
• the Carnot heat engine extracts latent heat from a high-temperature heat reservoir and discharges some lesser latent heat into a low-temperature heat reservoir associated with the biosphere. Due to the reversibility of a Carnot heat engine, the entropy associated with the discharged latent heat is the same as that associated with the extracted latent heat. The ability of the Carnot heat engine to perform thermomechanical work upon demand is due to the spontaneity of the irreversible exothermic chemical reaction (typically combustion) that generates the high-temperature heat reservoir. Combustion perturbs the biosphere by the discharge of heat energy into the atmosphere and, moreover, by the discharge of chemical by-products deleteriously perturbing the atmosphere.
• thermomechanical engines increase the entropy of the biosphere.
• the tipping point, due to thermomechanical engines, of an unnatural uncompensated increase in entropy of the biosphere, in regard to climate change, is argumentative at present. It is irrefutable, however, that the widespread proliferation of thermomechanical engines deleteriously perturbs the biosphere due to an ever-increasing entropy.
• the only means to remedy the deleterious increase in the entropy of the biosphere, by the performance of work upon demand, is the exploitation of the entropy equilibration conceived by Gibbs (1873): "It is required to find the greatest amount by which it is possible under these conditions to diminish the entropy of an external system. This will be, evidently, the amount by which the entropy of the body can be increased without changing the energy of the body or increasing its volume.” This is the Gibbs free entropy.
• the radiative generation of mobile electron-hole pairs is limited by the solar irradiance, such that the power density of a photovoltaic cell is way too small for direct energy conversion.
• the low power density of all known forms of renewable energy in the prior art is remedied by a novel and useful exploitation of the vibrational energy of the Planckian resonators of the artificial nuclei 104 in the phonovoltaic cell 400 in FIG. 21.
• An uncompensated increase in the entanglement entropy S en t during the isothermal phase transition B ⁇ C in the phonovoltaic cell 400 is responsible for a decrease in the entropy of the ambient, as prophesized by Gibbs (1873).
• the only way to perform work on demand in harmony with Earth's energy budget in FIG. 32 is to cause a decrease in the entropy of the biosphere that is compensated by the entropy increase associated with the work performed upon demand.
• the uniqueness of the phonovoltaic cell 400 in FIG. 21 is the performance of work on demand by an induced decrease in entropy of the biosphere, as will be discussed.
• the invention involves a new type of solid-state composition of matter derived from the heating of boron and silicon hydrides in the presence of hydrogen and, optionally, an oxidizing chemical agent.
• FIG. 34 shows a micrograph obtained by high-resolution transmission electron microscopy (HRTEM) of picocrystalline oxysilaborane 502 deposited on a monocrystalline (001) silicon substrate 501.
• the interfacial layer 503 is due to specific deposition conditions, as will be explained later hereinbelow.
• An HRTEM fast Fourier transform (FFT) image of the monocrystalline silicon substrate 501 is shown in FIG. 35.
• An FFT image of the picocrystalline oxysilaborane film 502 is shown in FIG. 36.
• the FFT image of the silicon substrate 501 in FIG. 35 is typical of a monocrystalline lattice with a long-range periodic translational order
• the FFT image of the picocrystalline oxysilaborane film 502 in FIG. 36 exhibits a short-range order that is not characteristic of a monocrystalline lattice or an amorphous glass - for reasons affecting embodiments of this invention.
• the HRTEM diffraction intensity of the monocrystalline silicon substrate 501 is graphed in FIG. 37 in terms of the interplanar lattice d-spacings between parallel Bragg planes of atoms supporting a constructive electron wave interference.
• the highest-intensity peak shown in FIG. 37 is associated with the interplanar lattice d-spacing of 3.135 A between parallel ⁇ 111 ⁇ planes of atoms in the monocrystalline silicon substrate 501.
• FIG. 39 a conventional ⁇ -2 ⁇ x-ray diffraction (XRD) pattern of a thin picocrystalline borane film, as shown in FIG. 39.
• XRD x-ray diffraction
• the angle of incidence ⁇ of the x-ray beam and the angle 2 ⁇ of the diffracted x-ray beam are both relatively constant and collectively varied together over the x-ray diffraction angle 2 ⁇ .
• a set of regularly-spaced lattice planes results in a sharp diffraction peak.
• the thin picocrystalline borane film scanned in FIG. 39 was also deposited over a monocrystalline (001) silicon substrate.
• the high-intensity peaks in FIG. 39 are associated with x-ray diffraction from regularly-spaced silicon lattice planes.
• GIXRD diffraction peaks are due to regularly-spaced lattice planes of atoms in the thin picocrystalline borane film - not the silicon substrate.
• a sharp low-intensity x-ray peak exists at 2 ⁇ 13.07° in FIG. 41.
• a picocrystalline borane film is not polycrystalline.
• a polycrystalline film is comprised of a large number of crystalline grains that are randomly ordered, such that all sets of regular interplanar lattice spacings are brought into the Bragg condition in any GIXRD scan by virtue of the random ordering of the polycrystalline grains. This is not the case in FIGS. 40 -41.
• a possible explanation of the structure of a picocrystalline borane film is, now, introduced by reconciling the experimental diffraction data with the theoretical symmetry analysis provided hereinabove.
• Boron ⁇ B exhibits a nuclear angular momentum 33 ⁇ 4, as well as, a large positive nuclear electric quadrupole moment of +0.111 x l0 ⁇ 2 e-cm 2 .
• Boron ⁇ B exhibits a nuclear angular momentum 3/2 3 ⁇ 4, as well as, a positive nuclear electric quadrupole moment of +0.0355 xl0 ⁇ 24 e-cm 2 .
• the naturally-occurring isotopes of boron are -20% gB and -80% gB.
• the center of gravity of the boron nuclei is shifted from the geometric center of the icosahedral faces. This tends to deform the symmetrical nuclear configuration of boron icosahedra. This deformation can be related to an isotopic enrichment discussed by Nishizawa, "Isotopic Enrichment of Tritium by Using Guest-Host Chemistry," in Journal of Nuclear Materials, Vol. 130, 1985, p.465.
• Nishizawa employed a guest-host thermochemistry to eliminate radioactive tritium from waste water at a nuclear facility by a crown ether and an ammonium complex.
• Ammonium NH 3 weakly trapped by a crown ether exists in a symmetrical triangle with the three hydrogen nuclei at the triangle corners and the center of gravity at the geometric center. The distance between the hydrogen nuclei along the triangular edges is 1.62 A. If one hydrogen atom is replaced by a tritium atom, the center of gravity is shifted by 0.28 A towards the tritium atom.
• a nanocrystalline solid is typically taken to be a polycrystalline solid with small grains, with the grain size being less than 300 nm. As the grain size is reduced, then the periodic translational order is of a shorter range and the x-ray diffraction peaks are broadened. Whereas any typical nanocrystalline material is void of any long-range order, the picocrystalline oxysilaboranes of this invention possess a short-range periodic translational order along with a long-range bond- orientational order that is believed to be due to the self- alignment of boron icosahedra with a nearly-symmetrical nuclear configuration.
• a picocrystalline borane solid is a solid, comprised of at least boron and hydrogen, that exhibits a long-range bond-orientational order due to sharp x-ray diffraction peaks when subjected to grazing-incidence x-ray diffraction (GIXRD).
• GIXRD grazing-incidence x-ray diffraction
• the intraicosahedral x-ray diffraction peaks in artificial nuclei 104 are broadened by a mixture of the two boron isotopes and ⁇ B. It is purposeful to more precisely define as to what is meant by "broad” and “sharp" x- ray diffraction peaks in preferred embodiments of this invention.
• Any sharp x-ray diffraction peak is characterized by a peak width at half intensity that is at least ten times smaller than the peak height.
• a broad x-ray diffraction peak is characterized by a peak width at half intensity that is greater than half the peak height.
• the extended three-dimensional network of the picocrystalline oxysilaboranes is formed by a translation through space of an irregular hexahedron.
• the fivefold symmetry of a regular icosahedron is incompatible with the fourfold symmetry of a regular hexahedron (cube), such that it is impossible to periodically translate a regular hexahedral unit cell, with icosahedral quantum dots at the vertices, over space in a translationally invariant manner. Symmetry breaking must occur in the irregular borane hexahedra 300 shown in FIG. 10.
• the fivefold rotational symmetry of the icosahedral artificial nuclei 104 is maintained, such that the fourfold symmetry of the irregular borane hexahedra 300 is therefore broken.
• Each irregular borane hexahedron 300 is formed by artificial nuclei 104 at the hexahedral corners.
• an artificial nucleus 104 is formed by a boron icosahedron, with a nearly-symmetrical nuclear configuration that preserves a fivefold rotational symmetry.
• novel electronic and vibrational properties due to a fivefold rotational symmetry of the artificial nuclei 104 are observable.
• the artificial nuclei 104 are comprised by the regular arrangement of first- and second-nearest neighbor natural boron atoms 102 that supports a short-range translational order.
• the artificial atoms 101 of the picocrystal- line oxysilaboranes confine a discrete quantization of energy levels in a region of space less than 300 pm.
• the discrete energy levels of the artificial nuclei 104 are fundamentally different from the discrete energy levels of natural atoms.
• spectroscopic principles of conventional chemistry The spectroscopic principles are framed by references to a book by Harris and Bertolucci, Symmetry and Spectroscopy, Oxford Univ. Press, 1978.
• the rotational, vibrational, and electronic degrees of freedom are totally intertwined in rovibronic energy levels which support a redistribution of electrons in response to microwave radiation.
• the artificial nuclei 104 have a detectable infrastructure.
• the self-alignment of the icosahedral faces of the artificial nuclei 104 is maintained in the presence of a random separation between the icosahedral body centers of the artificial nuclei 104.
• the alignment of natural atoms in molecules is typically described in terms of the bond angle of the atomic valence electrons. This property relates to the fact that a natural atom is void of any externally apparent nuclear infrastructure.
• the artificial nuclei 104 in the picocrystalline oxysilaboranes exhibit an infrastructure associated with a nearly-symmetrical icosahedron, with a boron nucleus 102 at each icosahedral vertex per FIG. 5.
• the boron nuclei 102 of an artificial nucleus 104 are chemically constituted by three-center bonds, such that a peak electron density ideally exists near the center of the eight icosahedral faces normal to the four k U1 ) wave vectors, per FIG. 5. It is significant that the artificial nuclei 104 comprise a caged boron icosahedron with no radial boron valence electrons.
• the artificial atoms 101 bond to natural atoms in picocrystalline oxysilaboranes by means of hydrogen atoms that are, in turn, bonded by a Debye force.
• the self-alignment of the artificial atoms 101 in the irregular borane hexahedra 300 results in the valence electrons of the hydrogen nuclei 103 being aligned along k ⁇ m ) wave vectors.
• the artificial atoms 101 are covalently bonded to the tetravalent atoms 303 along k in > wave vectors by means of hydrogen atoms.
• the bond angle between the artificial atoms 101 and the natural tetravalent atoms 303 is aligned along k ⁇ m ) wave vectors if the 20 icosahedral faces of the artificial atoms 101 are self-aligned and the icosahedral body centers randomly vary over a finite range.
• the short-range periodic translational order of the picocrystalline oxysila- boranes is characterized by a broad x-ray diffraction peak, under conventional ⁇ - 2 ⁇ x-ray diffraction, that exists, at least partly, within the diffraction angle range 32° ⁇ 2 ⁇ ⁇ 36°.
• the short-range periodic translational order of the artificial nuclei 104 supports the detection of the corners of the irregular borane hexahedra 300 forming the picocrystalline oxysilaboranes over a preferred compositional range.
• ⁇ -2 ⁇ x-ray diffraction by itself, cannot establish the self-alignment of artificial nuclei 104 in the picocrystalline oxysilaboranes.
• This deficiency can be remedied when conventional ⁇ -2 ⁇ x-ray diffraction is further augmented by a grazing-incidence x-ray diffraction (GIXRD).
• GIXRD grazing-incidence x-ray diffraction
• a method for making the oxysilaborane films of the present invention is a chemical vapor deposition causing the precipitation of a solid film by passing gas vapors containing boron, hydrogen, silicon, and oxygen over a heated substrate in a sealed chamber maintained at a pressure below that of the atmosphere.
• the preferred vapors are nitrous oxide N 2 0 and the lower-order hydrides of boron and silicon, with diborane B 2 H 6 and monosilane SiH 4 being the most preferred.
• Both hydrides can be diluted in a hydrogen carrier gas.
• a solid oxysilaborane film self-assembles over the substrate in a picocrystalline oxysilaborane under preferred conditions.
• a molybdenum susceptor can provide a solid substrate carrier that can be resistively or inductively heated.
• the substrate can be heated without any susceptor in a resistively-heated quartz tube. In all these methods there can exist heated surfaces (other than the intended deposition substratum) on which an oxysilaborane film is deposited.
• the substrate can be heated without a susceptor in a cold-wall reactor by radiative heat by halogen lamps in a low-pressure rapid thermal chemical vapor deposition that minimizes reactor outgassing from heated surfaces coated by prior depositions.
• a preferred method for preparing the picocrystalline oxysilaboranes of the present invention is described after the processing in various examples is considered.
• the deposition temperature exceeds ⁇ 350°C hydrogenation effects can be substantially eliminated.
• the thin picocrystalline solid can become significantly hydrogenated, such that hydrogen can be actively incorporated in chemical bonds.
• the relative atomic concentration of hydrogen in a picocrystalline oxysilaborane solid deposited below ⁇ 350°C is usually within the range of 10-25% depending on the degree of oxygen incorporation.
• an oxysilaborane solid substantially void of oxygen is more specifically referred to as a silaborane solid.
• Oxygen can be introduced into a picocrystalline oxysilaborane solid by either individual oxygen atoms or as part of water molecules. Any picocrystalline oxysilaborane solid containing water molecules is said to be hydrous while a picocrystalline oxysilaborane solid constituted by individual hydrogen and oxygen atoms with a relatively negligible amount of water is said to be anhydrous. It has been observed that hydrous picocrystalline oxysilaborane solids tend to undergo a change in color and stoichiometry over time due, apparently, to the change in the trapped water. Unless explicitly asserted otherwise, picocrystalline oxysilaborane solids in embodiments described hereinbelow are understood to be anhydrous.
• a deposition reactor is fitted with a load-lock chamber isolating the reaction chamber from the direct exposure to the ambient moisture.
• adsorbed moisture is difficult to fully eliminate during sample loading.
• hydration can alter the boron-to-silicon ratio.
• the boron-to-silicon ratio is ideally six.
• a preferred introduction of oxygen into anhydrous oxysilaborane is by means of nitrous oxide.
• the relative atomic concentration of boron in oxysilaborane amongst boron, silicon, and oxygen atoms is ideally ⁇ 83%. In the absence of any hydration effects, the relative atomic concentration of boron amongst boron, silicon, and oxygen atoms does not significantly exceed ⁇ 89%.
• the susceptibility to hydration depends, in part, on the relative oxygen atomic concentration in an oxysilaborane film and the method by which oxygen is introduced.
• Self-assembled picocrystalline oxysilaborane has characteristics that are useful in electronic integrated circuits using covalent semiconductors, such as monocrystalline silicon.
• the electronic properties of oxysilaborane solids can be modified in a controlled manner by processing conditions during wafer deposition.
• Picocrystalline oxysilaborane exhibits a long-range bond-orientational order.
• X- ray photoelectron spectroscopy (XPS) established the binding energy of the boron Is electron in picocrystalline oxysilaborane as ⁇ 188 eV, which is characteristic of chemical bonds in an icosahedral boron molecule.
• the oxygen Is electron binding energy, ⁇ 532 eV, is very similar to that of the oxygen Is electron binding energy in a metallic oxide and different from that of the oxygen Is electron in a solid.
• the silicon 2p electron binding energy in the oxysilaborane solids of this invention exhibits a sharp energy peak of ⁇ 99.6 eV over the compositional range. This is important for several reasons. First of all, the absence of two energy peaks in oxysilaborane implies that the Si-Si and Si-B bonds possess an identical binding energy. Secondly the measured binding energy of a silicon 2p electron in oxysilaborane is essentially that of monocrystalline silicon formed by tetrahedral chemical bonds in the diamond lattice.
• the silicon 2p electron binding energy in silicon dioxide is ⁇ 103.2 eV.
• oxysilaborane is deposited on amorphous silicon dioxide, there exists a distinct difference in the silicon 2p electron binding energy in the two compositions.
• the silicon 2p electron binding energy in oxysilaborane is that of monocrystalline silicon in a diamond lattice, despite being deposited over an amorphous oxide, due to the self-assembly of picocrystalline oxysilaboranes.
• picocrystalline oxysilaborane (B ⁇ H ⁇ Si y O ⁇ self-assembles in a preferred compositional range (2 ⁇ jc ⁇ 4, 3 ⁇ ,y ⁇ 5, 0 ⁇ z ⁇ 2) bounded by picocrystalline sila- borane (B 12 H 4 ) 4 Si4 at one compositional extreme and by picocrystalline oxysila-
• the first several examples teach the preferred processing of picocrystalline silaborane (B 12 H 4 ) 4 Si 4 with the help of two examples in which processing of silaboride and oxysilaborane in a broader range (0 ⁇ w ⁇ 5, 2 ⁇ x ⁇ 4, 3 ⁇ y ⁇ 5, 0 ⁇ z ⁇ 3) of (B 12 ) x Si y O z H u; is taught.
• the oxide was removed from the sample wafer by a hydrofluoric acid deglaze.
• the sample was inserted into a rapid thermal chemical vapor deposition (RTCVD) chamber of the type described by Gyurcsik et al. in "A Model for Rapid Thermal Processing," IEEE Transactions on Semiconductor Manufacturing, Vol. 4, No. 1, 1991, p.9. After loading the sample wafer upon a quartz ring, the RTCVD chamber was then closed and mechanically pumped down to a pressure of 10 mtorr.
• RTCVD rapid thermal chemical vapor deposition
• the reactant gas flow rate stabilized at a pressure of 3.29 torr, whereupon the tungsten-halogen lamps were turned on for 30 seconds and regulated so as to maintain the sample wafer at 605 °C.
• a thin silaboride solid 506 was deposited over the donor-doped region 505.
• the composition of the silaboride solid 506 was investigated by means of x-ray photoelectron spectroscopy (XPS).
• the binding energy of the boron Is electron was measured as being 187.7 eV, which is consistent with icosahedral boron.
• the binding energy of the silicon 2p electron was measured to be 99.46 eV, which is characteristic of monocrystalline (001) n-type silicon.
• An XPS depth profile of the silaboride solid 506 measured the relative atomic concentrations of boron and silicon within the silaboride solid 506 as being 86% and 14% respectively.
• Rutherford backscattering spectroscopy (RBS) measured the relative atomic concentrations of boron and silicon in the thin silaboride solid 506 as being 83.5% and 16.5% respectively.
• HFS hydrogen forward scattering
• RBS Rutherford backscattering spectroscopy
• a secondary ion mass spectroscopy (SIMS) analysis established the ⁇ B/ ⁇ B ratio of the silaboride solid 506 as the naturally-occurring ratio 4.03.
• the absence of any hydrogen or isotopic enrichment in the silaboride solid 506 of this example is due to the deposition temperature.
• a hydrogenation of silaborane can be realized when the deposition temperature is below ⁇ 350°C or when oxygen is introduced, as will be discussed in examples hereinbelow.
• the silaboride solid 506 of this example was confirmed by x-ray diffraction as being a pico crystalline boron solid.
• a GIXRD scan of the picocrystalline silaboride solid 506 of this example is shown in FIG. 43.
• Example 2 The procedure described above in Example 1 was carried out with the two exceptions that undiluted nitrous oxide N 2 0 was introduced at a flow rate of 704 seem and the flow rates of the two hydride gases were doubled.
• the vapor flow rate was stabilized at 9.54 torr, whereupon the tungsten- halogen lamps were turned on for 30 seconds, and regulated, in order to maintain the sample substrate 504 at 605°C.
• an oxysilaborane solid 507 was deposited upon the donor-doped region 505.
• the composition of the thin oxysilaborane solid 507 was evaluated by x-ray diffraction spectroscopy.
• a conventional ⁇ -2 ⁇ XRD scan of the thin oxysilaborane solid 507 is shown in FIG. 45.
• the picocrystalline boron solid 507 of the present example is not a borane solid but, rather, is much better characterized as an oxygen-rich composition (B 12 )2Si 3 5 0 2 5H in which the hydrogen atoms are, most likely, bonded to the oxygen atoms.
• a 75 mm diameter monocrystalline (001) -type silicon substrate 508 of a resistivity of 20 ⁇ -cm was loaded onto a quartz holder in the quartz tube, which was sealed and mechanically pumped down to a base pressure of 30 mtorr.
• a boron-rich film 509 was deposited on the (001) n-type silicon substrate 508 by introducing a 3% mixture, by volume, of diborane in hydrogen B 2 H 6 (3%)/H 2 (97%) at the flow rate of 180 seem and a 10% mixture, by volume, of monosilane in hydrogen SiH 4 (lO%)/H 2 (90%) at a flow rate of 120 seem.
• the gas flow rates stabilized at a deposition pressure of 360 mtorr.
• the motorized heating element was transferred over the sample.
• the deposition temperature was stabilized at 230°C after a ⁇ 20 minute temperature ramp due to the thermal mass of the quartz tube and the quartz sample holder.
• the pyrolysis was sustained for 8 minutes at 230°C, whereupon the motorized heating element was retracted and the reactive gases were secured.
• the relative atomic concentrations of boron and silicon in the silaborane film 509 were measured by different types of spectroscopy. [0217] An x-ray photoelectron spectroscopy (XPS) depth profile of the sila- borane film 509 was performed.
• the oxygen in the silaborane film 509 is due to an outgassing of water vapor from the quartz walls.
• FIG. 48 shows the relative atomic concentrations of boron, silicon and oxygen in the silaborane solid 509 as being respectively: 85%, 14%, and 1%.
• the binding energy of the boron Is electron was 187 eV, which is characteristic of the bonds in icosahedral boron molecules.
• the XPS binding energy of the silicon 2p electron was 99.6 eV, which is characteristic of the silicon 2p electron in (001) monocrystalline silicon.
• the XPS binding energy of the oxygen Is electron was measured as 532 eV.
• a depth analysis of the solid 509 by Rutherford backscattering spectroscopy (RBS) measured the relative bulk atomic concentrations of boron and silicon as 82.6% and 17.4% respectively.
• the Auger electron spectroscopy (AES) depth profile in FIG. 49 shows the relative atomic concentrations of boron, silicon, and oxygen in the silaborane solid 509 as being respectively: 73.9%, 26.1% and 0.1%.
• the thickness of the solid 509 was established by XPS, AES, and RBS as 998A, 826A, and 38 ⁇ .
• the relative bulk atomic concentrations of boron, hydrogen and silicon were all established by RBS/HFS depth profiles of the silaborane solid 509 of this example as: 66.5%, 19.5%, and 14.0%.
• a secondary ion mass spectroscopy (SIMS) depth profile was carried out in order to establish the existence of any isotopic enrichment.
• Example 3 An iso- topic enrichment of boron ⁇ B relative to boron ⁇ B was proven by the SIMS depth profile. Whereas the naturally-occurring gB/ gB ratio is 4.03, the SIMS analysis measured the ⁇ B/ ⁇ B ratio in the silaborane solid 509 as 3.81.
• the film in Example 3 is referred to as a silaborane solid 509 since the small relative atomic concentration of oxygen is believed to be in the form of water. As a result, this film is better referred to as a hydrous silaborane solid 509.
• the hydrous silaborane solid 509 is a picocrystalline borane solid by the definition hereinabove.
• the conventional ⁇ -2 ⁇ XRD diffraction pattern of the hydrous silaborane solid 509 in FIG. 39 is substantially that of the oxysilaborane solid 507 in FIG. 45
• the picocrystalline boron solids are fundamentally distinguished by the isotopic enrichment of boron relative to boron ⁇ B . This distinction impacts preferred embodiments of this invention.
• One objective of the present invention is to establish a novel genus of self-assembled picocrystalline oxysilaboranes promoting a redistribution of electrons amongst rovibronic energy levels in response to microwave radiation due to an uncompensated increase in entropy characterized by an isotopic enrichment of boron relative to boron ⁇ B .
• the novelty and utility of such a redistribution of electrons by microwave radiation can be further appreciated by other examples.
• a 100 mm diameter monocrystalline (001) / ⁇ -type silicon substrate 510 with a resistivity of 30 ⁇ -cm was inserted onto a resistively- heated molybdenum susceptor in an EMCORE D-125 MOCVD reactor by a load- lock system that isolated the deposition chamber from the ambient.
• the chamber was pumped below 50 mtorr, whereupon a 3% mixture, by volume, of diborane in hydrogen B 2 H 6 (3%)/H 2 (97%) at the flow rate of 360 seem and a 2% mixture, by volume, of monosilane in hydrogen SiH 4 (2%)/H 2 (98%) at a flow rate of 1300 seem were introduced into the chamber, after which the reactant gases were permitted to mix.
• the chamber pressure was regulated at 9 torr and the molybdenum susceptor was rotated at 1100 rpm.
• the substrate temperature was increased to 280°C by the resistively- heated rotating susceptor.
• the chemical reaction was allowed to proceed for 5 minutes, whereupon the susceptor heating was arrested and the sample was allowed to cool to below 80°C before removing it from the deposition chamber.
• a thin film 511 with a polymeric semitransparent color was deposited upon the substrate 510, as shown in FIG. 50.
• the silaborane solid 511 thickness was measured by variable-angle spectroscopic ellipsometry to be 166 nm.
• the silaborane solid 511 was smooth with no signs of a grain structure.
• the silaborane solid 511 did not exhibit visible hydration effects.
• silaborane solid 511 of this example is very similar to the silaborane solid 509 in Example 3 except that the silaborane solid 511 of this example did not exhibit measurable hydration effects. Electrical characteristics of the silaborane solid 511 were measured by an HP-4145 parameter analyzer, with sweep signals by a mercury probe. Linear and log-log graphs of the current-voltage characteristics of the silaborane solid 511 are shown in FIGS. 52 -53. The nonlinear current-voltage characteristics of the silaborane solid 511 are due to a space-charge-limited conduction current which deviates from Ohm's law beyond an onset of relaxation in accordance with FIG. 53.
• Mott and Gurney Electronic Processes in Ionic Crystals, Oxford University Press, second edition, 1948, pp. 168-173.
• Mott and Gurney developed that a space-charge-limited current density J between electrodes, intervened by a solid dielectric, quadratically varies with an impressed electromotive force V, where d is the electrode separation, ⁇ is the charge mobility, and ⁇ is the permittivity of the solid-state dielectric or semiconductor.
• the Mott- Gurney law is satisfied whenever a unipolar excess mobile charge exists due to a nonvanishing divergence of the electric field per Gauss' law.
• the space-charge-limited conduction current in the picocrystalline oxysilaboranes is due to a charge conduction mechanism not heretofore known in the prior art.
• a conduction current density in a solid is conventionally bounded by
• Example 4 The procedure described in Example 4 was carried out with the sole exception that nitrous oxide was introduced at a flow rate of 40 seem.
• a thin oxysilaborane film 512 with a polymeric semitransparent color was deposited over the (001) monocrystalline >-type silicon substrate 510.
• the oxysilaborane film thickness was measured by variable-angle spectroscopic ellipsometry as being 159 nm.
• the XPS depth profile in FIG. 55 established the relative atomic concentrations of boron, silicon, and oxygen in the bulk oxysilaborane solid 512 as respectively being: 88.0%, 10.4%, and 1.6%.
• the inclusion of oxygen transformed the silaborane solid 511 in FIG. 50 of Example 4 into the oxysilaborane solid 512 in FIG. 54 of this example.
• the incorporation of oxygen altered the oxysilaborane solid 512 of this example relative to the silaborane solid 511 of Example 4.
• the electrical impedance of the oxysilaborane film 512 of the present example was measured by an HP-4145 parameter analyzer, with the sweep signals provided by a mercury probe. Linear and log-log graphs of the impedance characteristics of the oxysilaborane solid 512 of this example are respectively shown in FIGS. 56-57.
• the impedance of the oxysilaborane solid 512 of the present example increased relative to the silaborane solid 511 in Example 4. Whereas the space- charge-limited current in the silaborane solid 511 saturated at a quartic current- voltage characteristic, the space-charge-limited current in the oxysilaborane solid 512 of this present example saturated at a quintic current-voltage characteristic, as shown FIG. 57.
• the space-charge current is limited by mobile charge drift.
• Example 5 The procedure described in Example 5 was carried out with a single exception that the flow rate of the nitrous oxide was increased from 40 seem to 80 seem.
• the thickness of the oxysilaborane solid 512 of this example was measured by variable-angle spectroscopic ellipsometry as being 147 nm.
• the XPS depth profile in FIG. 58 established the relative atomic concentrations of boron, silicon, and oxygen in the bulk oxysilaborane solid 512 as respectively: 88.1%, 9.5%, and 2.5%.
• the relative atomic concentration of boron in the oxysilaborane solid 512 of this example is the same as the oxysilaborane solid 512 within Example 5.
• the atomic concentration of silicon in the oxysilaborane solid 512 of this example decreased relative to that of the oxysilaborane solid 512 in Example 5.
• the bulk atomic concentration of oxygen in the oxysilaborane solid 512 of this example was increased relative to that of the picocrystalline oxysilaborane solid 512 in Example 5.
• Example 6 The procedure described in Example 6 was carried out with the sole exception that the flow rate of the nitrous oxide was increased from 80 seem to 100 seem.
• the thickness of the oxysilaborane solid 512 of this example was measured by variable-angle spectroscopic ellipsometry as 140 nm.
• the XPS depth profile in FIG. 61 measured the relative atomic concentrations of boron, silicon, and oxygen in the oxysilaborane solid 512 as being respectively: 85.9%, 10.7%, and 3.4%.
• the impedance of the oxysilaborane solid 512 of this example was measured by an HP- 4145 analyzer, with the two sweep signals obtained by a mercury probe.
• FIGS. 62-63 Linear and log-log graphs of the current-voltage characteristics of the oxysilaborane solid 512 of this example are shown in FIGS. 62-63.
• the oxysilaborane solid 512 of this example exhibited a slightly higher impedance than that of Example 6.
• Example 7 The procedure described in Example 7 was carried out with a sole exception that the flow rate of nitrous oxide was increased from 100 seem to 300 seem.
• the thickness of the thin oxysilaborane solid 512 of this example was measured by variable-angle spectroscopic ellipsometry as being 126 nm.
• the XPS depth profile in FIG. 64 measured the relative atomic concentrations of boron, silicon, and oxygen in the oxysilaborane solid 512 of this example as: 83.4%, 10.5%, and 6.2%.
• the impedance of the oxysilaborane solid 512 was measured by an HP-4145 parameter analyzer.
• the linear and log-log graphs of the impedance characteristics of the oxysilaborane solid 512 of this example are shown in FIGS. 65-66.
• Example 8 The procedure in Example 8 was carried out with the exception that the nitrous oxide flow rate was increased from 300 to 500 seem.
• the thickness of the thin oxysilaborane solid 512 of this example was measured by variable-angle spectroscopic ellipsometry as 107 nm.
• the XPS depth profile in FIG. 67 established the relative atomic concentrations of boron, silicon and oxygen in the bulk oxysilaborane solid 512 of this example as being: 82.4%, 10.0%, and 7.6%.
• RBS and HFS analysis established the bulk relative atomic concentrations of boron, hydrogen, silicon, and oxygen: 66%, 20%, 9%, and 5%.
• the relative atomic concentration of oxygen is near its RBS detection limit.
• the impedance of the oxysilaborane solid 512 of this example was measured by an HP-4145 parameter analyzer, with sweep signals obtained by a mercury probe. Linear and log-log graphs of the impedance characteristics of the oxysilaborane solid 512 of this example are in FIGS. 68-69.
• the oxysilaborane solid 512 of this example is oxygen-rich, such that it does not exist in the preferred compositional range (2 ⁇ x ⁇ 4, 3 ⁇ y ⁇ 5, 0 ⁇ z ⁇ 2) of picocrystalline oxysilaborane (B ⁇ H ⁇ Si y O., but is contained in a broader compositional range (0 ⁇ i > ⁇ 5, 2 ⁇ ⁇ ; ⁇ 4, 3 ⁇ ,y ⁇ 5, 0 ⁇ z ⁇ 3) of oxysilaborane (B ⁇ Si ⁇ O ⁇ H ⁇ .
• Monocrystalline silicon was epitaxially deposited over a (001) boron- doped j9-type monocrystalline substrate 521 with a 100 mm diameter and 525 ⁇ thickness.
• the resistivity of the degenerate monocrystalline silicon substrate 521 was 0.02 ⁇ -cm, which corresponds to an acceptor concentration of ⁇ 4xl0 18 cm -3 .
• a nondegenerate / ⁇ -type monocrystalline silicon layer 522 was deposited on the silicon substrate 521.
• the epitaxial silicon layer 522 had a thickness of 15 ⁇ and a resistivity of 2 ⁇ -cm, which corresponds to an acceptor impurity concentration of ⁇ 7xl0 15 cm -3 . All oxide was removed by a hydrofluoric acid deglaze.
• the silicon substrate 521 was inserted onto a resistively-heated susceptor in an EMCORE MOCVD reactor by a load-lock system that isolated the deposition chamber from the ambient.
• the deposition chamber was pumped below 50 mtorr, whereupon a 3% mixture by volume of diborane in hydrogen B 2 H 6 (3%)/H 2 (97%) at the flow rate of 150 seem and a 2% mixture by volume of monosilane in hydrogen SiH 4 (2%)/H 2 (98%) at the flow rate of 300 seem were introduced into the deposition chamber.
• Nitrous oxide N 2 O was introduced at a flow rate of 100 seem. [0238] The gases were permitted to mix before entering into the deposition chamber.
• the chamber pressure was regulated at 1.5 torr while the susceptor was rotated at 1100 rpm.
• the substrate temperature was increased to 230°C for 2 minutes.
• the susceptor temperature was yet further increased to 260°C, whereupon it stabilized and the chemical reaction was permitted to proceed for 12 minutes.
• the susceptor heating was secured and the sample was permitted to cool below 80°C in the reactant gases before it was removed from the deposition chamber.
• An oxysilaborane film 523 was deposited. The thickness was measured by variable-angle spectroscopic ellipsometry as being 12.8 nm. Due to the thickness, the oxysilaborane film 523 showed no coloration.
• Linear current-voltage characteristics of the / ⁇ -isotype electrochemical rectifier 520 of this example are shown at two distinct current-voltage ranges in FIGS. 71-72.
• the electrochemical rectifier 520 achieves an asymmetrical electrical conductance without the aid of a p-n junction by means of a variation in the surface electrochemical potential.
• FIG. 71 a considerably greater current flows when the cathode electrode 524 is negatively-biased (forward-biased) relative to the anode electrode 525.
• the cathode electrode 524 is positively-biased (reverse-biased) relative to the anode electrode 525, the much smaller current increases with an increased reverse bias beyond ⁇ 1V.
• the increased reverse-bias current is believed to be due to deleterious interfacial effects due to non-ideal processing conditions.
• Forward-bias and reverse-bias logarithm current-voltage plots are represented in FIGS. 73 -74.
• the asymmetrical current conduction is due to a built-in field.
• Example 10 The procedure described in Example 10 was carried out with the sole exception that the flow rate of nitrous oxide N 2 0 was increased from 20 seem to 65 seem.
• the thickness of the oxysilaborane film 523 of this example was measured by variable-angle spectroscopic ellipsometry as 12.4 nm.
• the electrical characteristics of the j9-isotype electrochemical rectifier 520 of this example were measured by an HP-4145 parameter analyzer, with sweep signals obtained from the anode and cathode electrodes 525 and 524 by means of microprobes.
• the linear current- voltage characteristics of the / ⁇ -isotype electrochemical rectifier 520 of this present example are shown at two different ranges in FIGS. 75-76.
• Example 11 The procedure described above in Example 11 was carried out with the exception that the reaction time at 260°C was decreased from 12 minutes to 6 minutes.
• the thickness of the oxysilaborane film 523 of this present example was measured by variable-angle spectroscopic ellipsometry as 7.8 nm.
• the electrical characteristics of the / ⁇ -isotype electrochemical rectifier 520 of this example were measured by an HP-4145 parameter analyzer, with sweep signals obtained from the anode and cathode electrodes 525 and 524 by two microprobes.
• Linear current- voltage characteristics of the / ⁇ -isotype electrochemical rectifier 520 of the present example are shown at three different current-voltage ranges in FIGS. 79 -81.
• the forward-bias and reverse-bias logarithm current-voltage characteristics are presented in FIGS. 82-83.
• the rectification properties of this example are improved relative to Examples 10 -11 due, in large part, to the thinner film 523.
• Example 12 The procedure in Example 12 was carried out with the exception that nitrous oxide N 2 0 was never introduced.
• the thickness of the silaborane film 526 represented in FIG. 84 was measured by variable-angle spectroscopic ellipsometry as being 11.4 nm.
• the electrical characteristics of the device 520 were measured by an HP-4145 parameter analyzer, with the sweep signals obtained from the anode and cathode electrodes 525 and 524 by means of microprobes.
• the linear current- voltage characteristics of the device 520 are shown in FIGS. 85-86.
• the forward- bias and reverse-bias logarithm current-voltage plots are shown in FIGS. 87-88.
• a forward-bias current in the / ⁇ -isotype electrochemical rectifier 520 in Example 11 increases linearly with the bias voltage at a low current and increases with a quartic voltage dependence beyond the relaxation voltage.
• the forward-bias current-voltage characteristic of the rectifier 520 in Example 11 is space-charge-limited by the oxysilaborane film 523 beyond a relaxation voltage, whereupon the transit time is less than the relaxation time.
• the conduction current represented by the log-log graph in FIG. 77 is characteristic of an injected charge plasma.
• the electric current density and voltage vary linearly until a sufficiently high level of charge injection results in a space-charge-limited current density due to a breakdown in charge neutrality.
• High-level charge injection in a semiconductor tends to result in a quadratic dependence of the space-charge-limited current density upon voltage while a high-level charge injection in a dielectric tends to result in a cubic dependence of a space-charge-limited current density upon voltage.
• the principal difference between a semiconductor and a dielectric is that the former is characterized by a large mobile-charge concentration, of a negative or a positive polarity, while the latter is characterized by a negligible mobile-charge concentration.
• the log-log current-voltage characteristic of the rectifier 520 shown in FIG. 77 should be characteristic of the charge plasma injected into a dielectric since the oxysilaborane film 523 in Example 11 has a bulk composition of
• a silicon p-i-n diode with an intrinsic silicon region length of 4 mm exhibits a space-charge- limited current-voltage characteristic with a cubic dependency of the current density on the impressed voltage beyond a relaxation voltage of 10 V.
• the length of the intrinsic silicon region of the p-i-n diode is decreased to approximately 1 mm, the current density varies exponentially with an impressed voltage due to a dominance of mobile-charge diffusion.
• the electrochemical rectifier 520 in Example 11 possesses a drift space-charge-limited current-voltage characteristic in the thin oxysilaborane film 523 of only 12.4 nm, which has a bulk
• the extrinsic mobile-charge concentration of self-assembled picocrystalline oxysilaborane (B ⁇ H ⁇ Si y Q., over a preferred compositional range (2 ⁇ x ⁇ 4, 3 ⁇ y ⁇ 5, 0 ⁇ z ⁇ 2) is ideally constant near p Q ⁇ 10 18 cm -3 due to the nuclear electric quadrupole moment of the boron icosahedra with an ideally symmetrical nuclear configuration.
• the extrinsic concentration p Q corresponds to the impurity doping concentration in monocrystalline silicon attributed to an onset of bandgap narrowing.
• Picocrystalline oxysilaborane (B ⁇ H ⁇ Si ⁇ O ⁇ is a novel composition in that it exhibits a closed-shell electronic configuration and also an extrinsic mobile- charge concentration near the onset of bandgap narrowing in silicon.
• a key element of charge conduction in picocrystalline oxysilaborane ( 12 ii 4 ) x Si y O z over the preferred compositional range (2 ⁇ x ⁇ 4, 3 ⁇ y ⁇ 5, 0 ⁇ z ⁇ 2) is an invariant extrinsic charge concentration p Q resulting from the nuclear electric quadrupole moment of the boron icosahedra and, as a result, is not affected by the conventional semiconductor impurity doping.
• the extrinsic charge concentration p 0 is not affected by the incorporation of oxygen in an oxysilaborane film.
• Eqs. (66)-(67) are combined to obtain the following relation.
• the relaxation time ⁇ depends upon both the charge mobility ⁇ and the extrinsic charge concentration p Q
• the relaxation voltage V T depends on the latter - which is invariant in picocrystalline oxysilaborane (B ⁇ H ⁇ Si ⁇ O ⁇ over the preferred compositional range (2 ⁇ x ⁇ 4, 3 ⁇ y ⁇ 5, 0 ⁇ z ⁇ 2).
• picocrystalline silaborane j9-(B 12 H 4 ) 3 Si 5 solid 526 deposited per Example 13 has a thickness of 11.4 nm and a relaxation voltage V T ⁇ 0.2V in FIGS. 87-88.
• the picocrystalline oxysilaborane p- B 12 ⁇ ) 2 8 ⁇ 4 ⁇ 2 solid 523 per Example 11 exhibits a thickness of 12.4 nm and relaxation voltage V T ⁇ 0.2V in FIGS. 77-78.
• an open-circuit electric field E emanates from oxysilaborane dications in region 402 and terminates upon silaborane dianions in region 401 of the phonovoltaic cell 400 in FIG. 21. Since field lines are associated with charge pairs and since the extension of the field is approximately two Debye lengths L B into region 402, the open-circuit electric field E between the conjoined regions 401 and 402 of the phonovoltaic cell 400 is given, by a first approximation, as follows:
• the electric field E per Eq. (70) is ⁇ 5 x 10 4 V/cm for a Debye length L of ⁇ 4 nm. Only if the thickness of the cathode region 402 of the phonovoltaic cell 400 in FIG. 21 is less than the diffusion length will the open- circuit electric field in Eq. (70) manifest itself, in part, as an open-circuit electromotive force V between the conjoined anode and cathode regions 401 and 402. At room temperature, the electrical energy stored in the electric field is ⁇ 39 meV. The electric field in Eq.
• the thinnest picocrystalline oxysilaborane film in the above examples is 7.8 nm in Example 12, the film thickness is not sufficiently thin that the space-charge-limited current density is, at least in part, due to mobile charge diffusion.
• a 100 mm diameter monocrystalline (001) / ⁇ -type silicon substrate 527 with a resistivity of 5 ⁇ -cm was loaded on a resistively-heated molybdenum susceptor in an EMCORE D-125 MOCVD reactor by a load-lock system which isolates the deposition chamber.
• the deposition chamber was pumped down below 50 mtorr, whereupon a 3% mixture, by volume, of diborane in hydrogen B 2 H 6 (3%)/H 2 (97%) at a flow rate of 150 seem along with a 2% mixture, by volume, of monosilane in hydrogen SiH 4 (2%)/H 2 (98%) at a flow rate of 300 seem were introduced into the deposition chamber.
• undiluted nitrous oxide N 2 0 was introduced at a flow rate of 20 seem.
• the reactant gases were allowed to mix together before entering into the deposition chamber.
• the chamber pressure was regulated at 1.2 torr while the susceptor was rotated at 1100 rpm.
• the substrate temperature was increased to 230°C by the resistively-heated susceptor, prior to further increasing the temperature.
• the susceptor temperature was further increased to 260°C, whereupon it stabilized and the chemical reaction was allowed to proceed for 12 minutes.
• the susceptor heating was secured and the sample was allowed to cool below 80°C in the reactant gases before it was removed from the deposition chamber. As shown in FIG.
• a thin oxysilaborane film 528 was deposited on the silicon substrate 527.
• the thickness of the oxysilaborane film 528 of this example was established by variable-angle spectroscopic ellipsometry as being 8.2 nm. The small thickness introduces deleterious anomalies in the oxysilaborane film 528.
• X-ray photoelectron spectroscopy (XPS) of the oxysilaborane film 528 of this example was impeded by the small thickness.
• XPS is a surface analytical method that can be used to establish depth profiles by an argon sputtering of the sample between a number of repeated surface measurements.
• the photoelectrons are not limited to the actual surface but, rather, can be emitted from depths below the surface of over 5.0 nm. In order to better improve the depth profile resolution, the takeoff angle was reduced to 20°, such that the escape depth of photoelectrons was on the order of 2.5 nm.
• an XPS depth profile of the oxysilaborane film 528 of this example in FIG. 90 established the relative bulk atomic concentrations of boron, silicon, and oxygen at the peak boron concentration as: 83.4%, 11.1%, and 5.5%.
• the composition at a peak boron concentration is in accordance with
• borane p- B 12 H4) 2 Si 4 0 2 measured by an XPS depth profile in this example relate to changes in the binding energy of the inner photoelectrons, especially the silicon 2p electron binding energy.
• the oxygen Is electron binding energy was measured as 531.5 eV at the surface, 531.4 eV near the middle of the oxysilaborane film 528 of this example, and 530.8 eV near the silicon substrate 527.
• the boron Is electron binding energy in this example was measured by XPS as 187.3 eV at the surface, 187.6 eV in the middle of the oxysilaborane film 528 of this example, and 187.6 eV near the silicon substrate 527.
• the above binding energies are nearly ideal.
• binding energies are consistent with the boron binding energy measured by XPS in the prior examples hereinabove. Quite different from all the other examples, however, is the existence of a double energy peak in the silicon 2p electron binding energy near the surface, with the lower peak being 99.7 eV.
• the binding energy of the silicon 2p electron is 99.3 eV in the middle of the oxysilaborane film 528 and near the silicon substrate 527.
• the binding energy of this single energy peak is in agreement with the single energy peak in prior examples disclosed hereinabove.
• a thermal processing profile of a picocrystalline oxysilaborane solid similar to this example is in FIG. 91. The temperature is represented along the ordinate and the elapsed run time along the abscissa in seconds. [0261] It is noteworthy in FIG. 91 that the cooling time is 12 minutes (from
• the film integrity can be improved by a more rapid cooling. It is known that an undesirable surface oxidation of the oxysilaborane film 528 of this example occurred during the sample cooling. This deleterious oxidation must be eliminated in the phonovoltaic cell 400 shown in FIG. 21. It is further known that excess oxygen and silicon are incorporated in the oxysilaborane film 528 near the silicon substrate 527 due to the native oxide and other adsorbed contaminants introduced during the temperature ramp to the preferred temperature. As shown in the high-resolution transmission electron micrograph (HRTEM) in FIG. 34, the deleterious interfacial layer 503 is ⁇ 2 nm thick. An interfacial layer impedes the successful operation of the phonovoltaic cell 400 shown in FIG. 21.
• HRTEM transmission electron micrograph
• the phonovoltaic cell 400 in FIG. 21 must be in situ processed at an invariant deposition temperature.
• the metal electrodes 403 in the phonovoltaic cell 400 are in situ deposited by an MOCVD deposition using a suitable aluminum precursor.
• a suitable aluminum precursor is trimethylamine alane (TMAA) H g AlN(CH g )3.
• TMAA trimethylamine alane
• the deposition of aluminum nano- wires by means of TMAA is discussed in detail by Benson et al., "Chemical Vapor Deposition of Aluminum Nanowires on Metal Substrates for Electrical Energy Storage Applications," ACS Nano 6 (l), pp. 118-125 (2012).
• a suitable substrate such as a silicon wafer can be inserted into an EMCORE D-125 MOCVD reactor, per Example 14, which is pumped down below 50 mtorr.
• Trimethylamine alane (TMAA) H 3 AlN(CH 3 )g is introduced into the deposition chamber by means of a hydrogen carrier gas at a flow rate of 50 seem.
• the deposition chamber pressure is regulated at 2-4 torr while the substrate is heated to ⁇ 230°C.
• the substrate temperature is maintained at ⁇ 230°C and the reaction is permitted to proceed for several minutes until a thin layer of picocrystalline silaborane j9-(B 12 H ) 3 Si 5 of ⁇ l-3 nm is deposited, whereupon undiluted nitrous oxide N 2 0 at a flow rate of 20 seem is abruptly introduced into the deposition chamber while the hydride gases remain flowing.
• the substrate temperature is maintained at ⁇ 230°C and the reaction is permitted to proceed for several minutes until a thin layer of picocrystalline
• the in situ deposition of a / ⁇ -isotype rectifier 404 can be repeated on an in situ basis so as to form the phonovoltaic cell 400 shown in FIG. 21 by an in situ MOCVD deposition resulting in a large number of / ⁇ -isotype rectifiers 404, said to be a phonovoltaic pile.
• An in situ phonovoltaic cell 400 comprises a phonovoltaic pile with 20-50 / ⁇ -isotype rectifiers 404.
• each / ⁇ -isotype rectifier 404 can be optimized at ⁇ 26 mV. Preferred embodiments of the invention sustain an open-circuit voltage.
• the Gibbs free entropy is the entropy by which a body or many-body system may be increased without changing its energy or increasing its volume. Following the initial direction of Gibbs (1873), the Gibbs free entropy is "represented geometrically by the distance of the point representing the initial state from the surface of dissipated energy measured parallel to the axis of [S in FIG. 93.
• the Gibbs free energy is widely used in the prior art in the equilibration of a nonequilibrium state.
• Preferred embodiments of this invention utilize Gibbs free entropy in a novel and useful manner. The Gibbs free energy and Gibbs free entropy are involved in the quantum thermodynamic cycle in FIG.
• the volume of the artificial nuclei 104 comprising the picocrystalline oxysilaboranes remains invariant in the operation of the phonovoltaic cell 400.
• the energy and temperature of the picocrystalline silaborane j9-(B 12 H 4 ) 3 Si 5 anode regions 401 are both invariant during the isothermal phase transition B ⁇ C.
• the decrease in the phase transition entropy Si rans is due to the Gibbs free entropy of artificial nuclei 104 in the picocrystalline silaborane j9-(B 12 H 4 ) 3 Si 5 anode region 401.
• the Gibbs free entropy in the form of an intraicosahedral entanglement entropy S ent ) undergoes an uncompensated increase, such that there is a quantum localization of said artificial nuclei 104 that is thus accompanied by a decrease in the phase transition entropy Si rans as prophesized by Gibbs (1873) in his development of the Gibbs free entropy.
• the ability to exploit the Gibbs free entropy in the phonovoltaic cell 400 is a consequence of the artificial nuclei 104 retaining an icosahedral symmetry due to a lifting of the polyatomic electronic orbital degeneracies by spin-orbit coupling in lieu of the lifting of polyatomic electronic orbital degeneracies by Jahn-Teller distortion in all other icosahedral boron-rich solids in the prior art. This is due, in turn, to a highly novel and useful Lorentz force initially conceived by Maxwell in 1861 that became permanently lost in the prior art soon thereafter.
• Equations (71a-f) comprise 6 vector equations that Maxwell specified in terms of 18 equations involving 18 Cartesian components.
• the scalar equation in Eq. (71g) is an expression of Gauss' law while the scalar equation in Eq. (71h) is the continuity equation.
• Maxwell expressed the general equations of the electromagnetic field in terms of 20 equations utilizing 20 variables.
• Maxwell There is an extremely important concept introduced by Maxwell which has been lost over the years in the prior art. Due to the profound impact of this lost concept on modern integrated circuits, a cogent discussion of Maxwell's lost concept is provided.
• Maxwell always expressed his equations of the electromagnetic field in terms of the vector potential A and scalar potential xp.
• VxE -B (72b)
• VxH D (72 c)
• VxE - ⁇ - Vx(Bxv) (73b) ot
• the instantaneous velocity v can be decomposed into two distinct velocities that were recognized by Maxwell in 1861-1865.
• any infinitesimal electromagnetic disturbance can be specified in terms of the velocity r due to the motion of an inextensible electromagnetic disturbance through space and, also, the phase velocity s due to the periodic oscillation of an electromagnetic disturbance.
• the generalization of Faraday's induction law by Maxwell yielded the magnetic component vxB of the Lorentz force, albeit not the conventional Lorentz force.
• examination of Maxwell's derivation manifests that the instantaneous velocity v is the phase velocity s, such that Eqs. (73 a-d) are:
• VxE - ⁇ - VxBxs (74b) ot
• VxH + V «Dr + VxDxs (74c) ot
• V.B 0 (74 d)
• VxE - ⁇ + Vxs xB (75b)
• VxH J + ⁇ - Vxs xD (75 c) ot
• VxE - ⁇ + Vxs xB (77) dt
• the artificial nucleus 104 is formed by the chemical fusion of twelve natural boron atoms into an icosahedron, with a nearly-symmetrical nuclear configuration, in which all of the 36 boron valence electrons occupy intraicosahedral bonding and antibonding suborbitals. As previously disclosed hereinabove, fusion necessarily involves a transformation of a quantity of matter into energy. In the artificial nucleus 104 in FIG. 5, a small quantity of matter is transformed into the "trembling motion" (zitterschul) of a Dirac quasiparticle. As derived in U. S. Provisional Application No. 62/591,848 and incorporated herein by reference, the
• the corresponding zitterschul frequency is much too high to contribute to a conduction of electrical action, it supports the spectral induction of valence electrons from the intraicosahedral bonding suborbitals into the intraicosahedral antibonding suborbitals due to the uncompensated increase in the intraicosahedral entanglement entropy S en i.
• FIG. 94 A a p-n anisotype rectifier 414 in the dark is shown in FIG. 94 A along with the / ⁇ -isotype rectifier 404 in FIG.94 B.
• the various dimensions are greatly exaggerated for the ease of presentation of novel concepts in these, and other related, figures.
• 94A is constituted by an acceptor-doped monocrystalline silicon p-Si anode region 411 and a conjoined donor-doped monocrystalline silicon n-Si cathode region 412.
• the regions are electrically contacted by two aluminum electrodes 413.
• Thermal equilibrium is established in the p-n anisotype rectifier 414 by the diffusion of mobile holes and mobile electrons between conjoined regions 411 and 412, such that an open-circuit electric field exists between immobile donor ions and acceptor ions.
• the open-circuit electric field lines between the immobile donor and acceptor ions in the p-n anisotype rectifier 414 reside in a depleted space-charge region in which the immobile charge concentration far exceeds the mobile charge concentration.
• the crystalline restoration force in the p-n anisotype rectifier 414 is mobile charge recombination.
• the open-circuit electric field in the / ⁇ -isotype rectifier 404 in FIG. 94 B prevails between mobile dications and dianions.
• the mobile dications and dianions in the / ⁇ -isotype rectifier 404 are due to a charge diffusion across the metallurgical junction of the picocrystalline silaborane p-(B 12 H4) 3 Si 5 anode region 401 and the picocrystalline oxysilaborane
• the open-circuit electric field lines between the mobile dications and dianions in the j9-isotype rectifier 404 reside within an accumulated space-charge region in which the mobile charge concentration far exceeds the immobile charge concentration.
• the crystalline restoration force in the j9-isotype rectifier 404 is a mobile charge generation. Since the thickness of the picocrystalline silaborane j9-(B 12 H ) 3 Si 5 anode region 401 and the picocrystalline oxysilaborane
• p- ⁇ 12 H ) 2 Si 0 2 cathode region 402 are both less than a Debye length, the anode potential floats below the cathode potential so as to arrest an open-circuit current in the j9-isotype rectifier 404 in FIG. 94 B.
• No open-circuit voltage is generated in the p-n anisotype rectifier 414 in the dark, due to the absence of mobile electron- hole pairs available for conduction. This is remedied by the radiative generation of mobile electron-hole pairs in FIG. 95 A in response to impinging radiation hv.
• the open-circuit electric field between immobile acceptor and donor ions in the p-n anisotype rectifier 414 separates mobile electron-hole pairs which randomly diffuse into the depleted space-charge region. This charge separation causes mobile holes to diffuse towards the anode electrode 413 and mobile electrons towards the cathode electrode 413. Since no current flow exists under open- circuit conditions, the anode potential floats above the cathode potential per FIG. 96 A. An electric current flow exists when an electrical load is impressed between the anode and cathode electrodes of the p-n anisotype rectifier 414 of the photovoltaic cell in FIG. 97 A and the / ⁇ -isotype rectifier 404 of the phonovoltaic cell in FIG. 97B. Whereas the open-circuit voltage of the p-n anisotype rectifier 414 is -0.6 V, the open-circuit voltage of the / ⁇ -isotype rectifier 404 is ⁇ 26 mV.
• the output voltage of the / ⁇ -isotype rectifier 404 of the phonovoltaic cell 404 is orders of magnitude lower than that of the p-n anisotype rectifier 414 of a photovoltaic cell. This disparity is very deceiving since the power density of a solid-state device typically varies many orders of magnitude due to a variation in the current density. It is in this regard that the contrary polarity difference between the p-n anisotype rectifier 414 and / ⁇ -isotype rectifier 404 is significant.
• This limitation in the reverse-bias current density delivered to an electrical load by the p-n anisotype rectifier 414 of a photovoltaic cell is entirely consistent with a limitation in solar irradiance.
• the maximum power density of a silicon photovoltaic cell is limited to less than 34 mW/cm 2 by the solar irradiance.
• the efficiency of a photovoltaic cell is fundamentally limited in that the crystalline restoration force of the p-n anisotype rectifier 414 is mobile charge recombination - which is contrary to the preferred crystalline restoration force of charge generation. This is due, in turn, to a limitation in the contact technology of a monocrystalline semiconductor that supports extended conduction and valence energy bands over space.
• Tamm-Shockley interface state density can be realized by terminating crystalline silicon regions with amorphous silicon dioxide films such that the surface electrochemical potential can be modulated, in device operation, throughout the forbidden energy region.
• a field-effect transistor uses the ability to modulate the electrical conductivity of a monocrystalline silicon surface by capacitively-coupled electrodes via an intervening silicon dioxide thin-film.
• any silicon dioxide must be removed from semiconductor contact regions due to the extremely high resistivity of silicon dioxide ⁇ 10 16 ⁇ -cm.
• the semiconductor surface is degenerately doped so as to form an isotype homojunction such that the semiconductor surface electrochemical potential is pinned in the conduction or valence energy band.
• a metal or a silicide can be alloyed to the degenerate semiconductor surface, such that mobile charges can tunnel through a potential barrier into the isotype homojunction.
• the isotype homojunction acts as an ohmic contact to any high-resistivity semiconductor region.
• this type of ohmic contact prevents the employment of a monocrystalline semiconductor in an electrochemical rectifier wherein the electrochemical potential varies between the external electrodes.
• Mobile charge conduction in the j9-isotype rectifier 404 is by means of hopping between the artificial nuclei 104 of the picocrystalline artificial borane atoms 101 with a mobility of ⁇ 0.01 cm 2 /V-sec. Although the phonovoltaic cell 400 delivers a current to an electrical load under forward-bias conditions, the current density is reduced due to the hopping mobility.
• FIG. 98 a projected manufacturing cost analysis of a phonovoltaic cell 400 is provided in FIG. 98.
• the phonovoltaic pile of j9-isotype rectifiers 404 in a phonovoltaic cell 400 is in situ deposited in an MOCVD reactor under computer control.
• the effective processing cost is taken to be the processing cost of the phonovoltaic pile of the phonovoltaic cell 400.
• the specific resistance due to the hopping mobility is assumed to be 100 ⁇ -cm 2 . It is believed that this specific resistance is subject to a reduction by a yet further engineering improvement.
• the power density of 6.76 W/cm 2 is more than 200 times greater than that of the p-n anisotype rectifier of a photovoltaic cell.
• the / ⁇ -isotype rectifier 404 of the phonovoltaic cell 400 can be in situ deposited, under computer control, in a phonovoltaic pile.
• the phonovoltaic pile in FIG. 98 is assumed to comprise 36 j9-isotype rectifiers 404.
• the Edison effect is the phenomenon of the flow of electric charge between a pair of metallic electrodes, within an evacuated region, when one such metallic electrode (said to be the cathode electrode) is heated above the other such metallic electrode (said to be the anode electrode) by a sufficiently large temperature difference.
• the solid-state Edison effect is the phenomenon of a flow of electric charge between two metallic electrodes, both being at the ambient temperature, that are intervened by a solid semiconductive material having two contiguous zones of different Seebeck coefficients and that cause a decrease in the entropy of the ambient by the flow of electric charge to any passive electrical load impressed, directly or indirectly, between said metallic electrodes.
• a transient electric charge flow can exist between contiguous material regions of different Seebeck coefficients, said electric charge flow is continuously sustained if, and only, the increase in the entropy of mixing between said regions is due, at least indirectly, to the spectral induction of valence electrons into higher-energy antibonding energy levels due to an infrared zitterschul resonance.
• Maxwell conceived spectral induction (albeit not by name) in 1861 in a seminal paper "On Physical Lines of Force,” no actual use of spectral induction has ever occurred in the prior art. This is due, in turn, to a heretofore inability to adequately exploit zitterschul in practical materials and devices.
• the phonovoltaic cell 400 exploits a near-infrared zitterzi resonance to move electric charge through space in a novel and useful way.
• Another preferred embodiment of this invention exploits the microwave zitterschul in Eq. (79b) to displace electrical action, but not electrical charge, through space in a way that generalizes Maxwell's displacement current.
• Maxwell's electrical action is displaced over space by an externally-impressed time-dependent periodic driving force
• electrical action is displaced herein by an intrinsic zitterschul.
• Maxwell expressed “Here then we have two independent qualities of bodies, one by which they allow of the passage of electricity through them, and the other by which they allow of electrical action being transmitted through them without any electricity being allowed to pass...
• electromotive force acts on a conductor, it produces a current which, as it meets with resistance, occasions a continual transformation of electrical energy into heat, which is incapable of being restored as electrical energy by any reversion of the process...
• we may conceive that the electricity in each molecule is so displaced that one side is rendered positively, and the other negatively electrical, but that the electricity remains entirely connected with the molecule, and does not pass from one molecule to another.”
• Maxwell's displacement current is not an actual current associated with the motion of electric charges over space but, rather, is a displaced electrical action due to a time-dependent electric field.
• the displacement of electric charge in a conductor is due to a time-independent electric field.
• An electric field E is, in general, a force per unit charge, such that charge displacement in a conductor in response to an electric field E constitutes a form of work that is accompanied by a Joule heating.
• Maxwell emphasized that charge monopole displacement in a conductor is always accompanied by the transformation of electrical energy into heat energy. The displacement of electricity involves an electromotive force, which has never been reconciled with ordinary mechanical force.
• the operation of the phonovoltaic cell 400 of this invention involves a displacement of electric charge through space by hopping between the artificial nuclei 104
• other preferred embodiments involve a novel displacement of electrical action through space with all valence electrons remaining in molecular bonds.
• the physical impact of the nuclear electric quadrupole moments of the natural boron atoms 102 must be eliminated.
• trace metallic impurities can be introduced at the same impurity concentration as that due to the nuclear electric quadrupole moments of the natural boron atoms 102, which is now clarified by an example.
• a silicon dioxide film 532 was deposited over a gallium arsenide substrate 531.
• the titanium film 533 and the gold film 534 were evaporated over the silicon dioxide film 532.
• the substrate 531 was loaded onto a resistively-heated susceptor in the D-125 MOCVD chamber of Example 14.
• the chamber was mechanically pumped below 50 mtorr, whereupon a 3% mixture by volume of diborane in hydrogen B 2 H 6 (3%)/H 2 (97%) at a flow rate of 360 seem and a 2% mixture by volume of monosilane in hydrogen SiH 4 (2%)/H 2 (98%) at a flow rate of 1300 seem were introduced into the deposition chamber.
• An oxysilaborane film 535 was deposited over the gold film 534, as represented in FIG. 100.
• the film thickness was measured by variable-angle spectroscopic ellipsometry to be 91.8 nm.
• the XPS depth profile in FIG. 101 established that the respective relative atomic concentrations of boron, silicon and oxygen within the oxysilaborane film 535 are: 85.2%, 10.0%, and 3.8%.
• SIMS secondary ion mass spectroscopy
• the SIMS depth profile in FIG. 102 established the gold atomic concentration as being ⁇ 10 18 cm -3 .
• An RBS and HFS analysis established the relative atomic concentrations of boron, hydrogen, silicon, and oxygen as respectively being: 70%, 17%, 10%, and 3%.
• Metal electrodes 536 and 537 were evaporated over the gold film, per FIG. 103, by evaporating aluminum through a shadow mask in a bell-jar evaporator.
• the current-voltage characteristics of the oxysilaborane film 535 were measured by an HP-4145 parameter analyzer, with the two sweep signals being obtained by microprobes positioned on the metal electrodes 536 and 537.
• FIG. 104 A graph of the current-voltage characteristics of the oxysilaborane film 535 is shown in FIG. 104.
• the current-voltage characteristics exhibited an ohmic conduction, with the 2.9 ⁇ resistance due to the microprobe measurement apparatus.
• the incorporation of gold as a trace impurity substantially modifies the electrical conductivity properties of the oxysilaborane film 535. It is believed that a logical explanation of the change in conduction due to a trace incorporation of a coinage metal such as gold may be given by way of Maxwell's development of electromagnetism. The reformulation of Maxwell's equations is fully described in
• VxE - 3 ⁇ 4 ⁇ (80b) dt
• VxH J + ⁇ 80 c >
• V.B 0 ( 80 d )
• Maxwell's displacement current supports a displacement of electromagnetic energy through space without an actual displacement of electric charge.
• the power flux density of radiation propagating through space by means of Maxwell's displacement current is represented by the Poynting vector ExH.
• the radiation power displaced through space must be provided by means of some sort of external periodic driving force. Maxwell's reformulated field equations are yet further generalized in Eqs.
• Eq. (83) The term ⁇ ⁇ the right side of Eq. (83) pertains to the microwave zitterschul described by Eq. (79b). As discussed hereinabove, the existence of a microwave zitterschul is not known in the prior art.
• the above relation in Eq. (83) represents a novel and useful phenomenon, referred to herein as the microwave zitterterrorism Aharonov-Bohm effect. It is believed that the microwave zitterschul Aharonov-Bohm effect generates a periodic driving force in picocrystalline oxysilaboranes which is capable of displacing an electromagnetic power density ExH through space without the aid of any outside agency.
• the scaling paradigm of integrated circuits in the prior art involves the planar scaling of covalently-bonded semiconductor regions wherein electric charge monopoles are displaced in extended energy bands in which the mean free path of electric charge monopoles is typically many orders of magnitude greater than the interatomic spacing of the host semiconductor lattice atoms.
• This type of electric charge monopole displacement exists in the back end of line (BEOL) fabrication as well as in the front end of line (FEOL) fabrication of integrated circuits.
• BEOL interconnects were transformed from aluminum to copper in the prior art.
• the mean free path of electrons in copper is 39 nm, such that a large increase in resistivity occurs as the copper line widths are scaled below 50 nm.
• a parasitic leakage current occurs when silicon transistor feature sizes are scaled below approximately 28 nm, owing to the fundamental inability to confine mobile electric charge monopoles within extended energy bands over space.
• a number of other deleterious scaling effects occur in response to attempts to confine mobile electric charge monopoles in extended energy bands in deep-nanoscale integrated circuits. What is needed is a new type of integrated electrical displacement that does not involve the actual displacement of electric charge monopoles over space.
• microwave zitterschul Aharonov-Bohm effect is useful.
• the electromagnetic power density ExH displaced through space by the microwave zitterschul Aharonov-Bohm effect is believed to support the spectral displacement current density Vxs xD without incurring any resistance associated with an actual displacement of electric charge.
• preferred embodiments of this invention are believed to ideally act as a room-temperature superconductor, so long as the effective current density does not exceed a certain maximum current density. It is yet further believed that said maximum current density is comparable to that of graphene.
• the picocrystalline oxysilaboranes of this invention are highly useful as BEOL interconnects in that, unlike graphene, the deposition of the picocrystalline oxysilaboranes is by a low-temperature, con- formal vapor-phase-deposition. It is believed that gold-doped picocrystalline silaborane, void of any oxygen, is most useful as a BEOL interconnect.
• An incorporation of a trace impurity concentration ⁇ 10 18 cm -3 of gold atoms in gold-doped picocrystalline silaborane can be realized by including a gold precursor in the formation gas resulting in the deposition of picocrystalline silaborane.
• Preferred gold precursors are volatile organometallic dimethyl gold (III) complexes, with dimethyl gold (III) acetate (CH 3 ) 2 Au(OAc) being a preferred such gold precursor.
• the gold precursor can be introduced into the formation gas by a hydrogen carrier gas in an MOCVD reactor.

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