Group-iv ordered alloys and superlattices strained to silicon with deterministic compositions and atomic configurations

Abstract

A semiconductor device comprises a Si substrate having a mono-terrace surface or multiple terrace surfaces; and multiple Group-IV elements epitaxially grown by chemical vapor deposition (CVD) and pseudomorphically strained to the Si substrate; wherein a chemical and isotopic composition of the multiple Group-IV elements, as well as atomic configuration in each atomic plane, are deterministically predefined through selection of CVD chemical precursors having a desired composition and atomic configuration to be adsorbed at a surface of the Si substrate and incorporated into a solid growth front of the multiple Group-IV elements.

Description

P AT E N T Docket No. QS3101GROUP-IV ORDERED ALLOYS AND SUPERLATTICES STRAINED TO SILICON WITH DETERMINISTIC COMPOSITIONS AND ATOMIC CONFIGURATIONSCross Reference To Related Applications

[0001] The present application claims priority to U. S. Provisional Patent Application No. 63 / 718,682, filed November 10, 2024, entitled " GROUP-IV ORDERED ALLOYS AND SUPERLATTICES STRAINED TO SILICON WITH DETERMINISTIC COMPOSITIONS AND ATOMIC CONFIGURATIONS," the disclosure thereof incorporated by reference herein in its entirety.Field

[0002] The disclosed technology relates generally to semiconductors, and more particularly to group-IV materials, their properties, and methods for their epitaxial growth with deterministic compositions and atomic configurations.Background

[0003] This invention pertains to Group-IV ordered alloys, Quantum Wells (QWs) and Quantum Barriers (QBs), and superlattices (SLs), epitaxially grown by chemical vapor deposition (CVD), strained to silicon surfaces. In particular, it pertains to the possibility of the epitaxial growth of ordered alloy layers with specific chemical and / or isotopic compositions for each atomic plane, and atomic configurations within those planes, that are deterministically pre-defined. This is accomplished through the choice of suitable chemical precursors which possess bonds between elements that will be adsorbed and incorporated in the crystal as the epitaxial growth front progresses.

[0004] Depending on the lattice mismatch with respect to the silicon surface, and epitaxial growth conditions, the critical thickness of some layers can be several tens of nanometers thick, while others have a much smaller critical thickness, for example just a few atomic planes. The layers with larger critical thickness can be used to fabricate certain regions of devices, such as the channel and / or source and / or drain regions of MOSFETs, or the base and / or emitter regions and / or collector of HBTs, or the photo-absorption region of photodiodes, or the photo-absorption and / or gain regions of photodiodes with internal gain, or the light-emitting region and / or cladding layers of light-emitting diodes and / or LASERS, etc.

[0005] The layers with the smaller critical thickness can be used as "building blocks" of more complex stacked layer structures, comprising layers under tensile strain and layers under compressive strain, and possibly strain-neutral layers as well, to achieve varying degrees of strain balancing, dependingP AT E N T Docket No. QS3101 on the thickness and lattice mismatch of each type of layer (i.e., building block). These building blocks, when deposited in particular sequences, can form ordered alloys, QWs / QBs, periodic SLs, aperiodic or quasiperiodic SLs, with desirable electronic, and / or photonic, and / or phononic, and / or piezoelectric properties.

[0006] The incorporation of certain chemical species in specific atomic planes and atomic configurations of a layer stack, uniquely enabled by the use of specific precursors, can induce asymmetry / anisotropy between the two in-plane directions (i.e., directions parallel to the substrate). The deterministic control of such asymmetry / anisotropy across multiple atomic planes of a layer stack, can induce chirality in the electronic, and / or photonic, and / or phononic properties. This induced chirality can be incorporated into ordered alloys, QWs / QBs, periodic SLs, and aperiodic / quasiperiodic SLs. In the following the nomenclature used to describe the composition of QWs, implicitly assumes periodic boundary conditions, i.e., the existence of multiple QWs separated by sufficiently thick QBs, to avoid coupling of electron or hole wavefunctions between the nearest QWs.Brief Description of the Drawings

[0007] FIG. 1A: Table 1A with Zinc-Blende (ZB) cells of group-IV elements and exemplary precursors for epitaxial growth of the corresponding cells.

[0008] FIG. IB: Table IB with 5-atom tetrahedral cells of group-IV elements and exemplary precursors for epitaxial growth of the corresponding cells.

[0009] FIG.2A: Table 2A with lattice structure data for fully relaxed (in all directions) ZB cells of group-IV elements, and also with the corresponding key band structure data.

[0010] FIG. 2B: Table 2B with lattice structure data for fully relaxed (in all directions) 5-atom tetrahedral cells of group-IV elements, and also with the corresponding key band structure data.

[0011] FIG. 3A: Table 3A with lattice structure data for ZB cells of group-IV elements strained to Si (0 01) surfaces, and also with the corresponding key band structure data.

[0012] FIG. 3B: Table 3B with lattice structure data for 5-atom tetrahedral cells of group-IV elements strained to Si (001) surfaces, and also with the corresponding key band structure data.

[0013] FIG. 4A: Table 4A with lattice structure data for ZB cells of group-IV elements strained to Si (1 10) surfaces, and also with the corresponding key band structure data.

[0014] FIG. 4B: Table 4B with lattice structure data for 5-atom tetrahedral cells of group-IV elements strained to Si (110) surfaces, and also with the corresponding key band structure data.P AT E N T Docket No. QS3101

[0015] FIG. 5A: Table 5A with lattice structure data for ZB cells of group-IV elements strained to Si (1 11) surfaces, and also with the corresponding key band structure data.

[0016] FIG. 5B: Table 5B with lattice structure data for 5-atom tetrahedral cells of group-IV elements strained to Si (111) surfaces, and also with the corresponding key band structure data.

[0017] FIG. 6A is a band structure plot of C for a fully relaxed diamond crystalline cell. In the structure plots, the blue dots represent the valence band energy eigenvalues, and the red dots represent the conduction band energy eigenvalues (all in eV units).

[0018] FIG. 6B is a band structure plot of C for a diamond crystalline cell strained to a Si (001) surface.

[0019] FIG.6C is a band structure plot of C for a diamond crystalline cell strained to a Si (110) surface.

[0020] FIG.6D is a band structure plot of C for a diamond crystalline cell strained to a Si (111) surface.

[0021] FIG. 7A is a band structure plot of Si for a diamond crystalline cell using experimental crystal data.

[0022] FIG. 7B is a band structure plot of Si for a diamond crystalline cell strained to a Si (001) surface.

[0023] FIG.7C is a band structure plot of Si for a diamond crystalline cell strained to a Si (110) surface.

[0024] FIG. 7D is a band structure plot of Si for a diamond crystalline cell strained to a Si (1 1 1) surface.

[0025] FIG. 8A is a band structure plot of Ge for a fully relaxed diamond crystalline cell.

[0026] FIG. 8B is a band structure plot of Ge for a diamond crystalline cell strained to a Si (0 0 1) surface.

[0027] FIG. 8C is a band structure plot of Ge for a diamond crystalline cell strained to a Si (1 1 0) surface.

[0028] FIG. 8D is a band structure plot of Ge for a diamond crystalline cell strained to a Si (1 1 1) surface.

[0029] FIG. 9A is a band structure plot of Sn for a fully relaxed Diamond crystalline cell.

[0030] FIG. 9B is a band structure plot of Sn for a diamond crystalline cell strained to a Si (0 0 1) surface.

[0031] FIG. 9C is a band structure plot of Sn for a diamond crystalline cell strained to a Si (1 1 0) surface.

[0032] FIG. 9D is a band structure plot of Sn for a diamond crystalline cell strained to a Si (1 1 1) surface.P AT E N T Docket No. QS3101

[0033] FIG. 10A is a band structure plot of Pb for a fully relaxed diamond crystalline cell.

[0034] FIG. 10B is a band structure plot of Pb for a diamond crystalline cell strained to a Si (0 0 1) surface.

[0035] FIG. 10C is a band structure plot of Pb for a diamond crystalline cell strained to a Si (1 1 0) surface.

[0036] FIG. 10D is a band structure plot of Pb for a diamond crystalline cell strained to a Si (1 1 1) surface.

[0037] FIG. 11A is a band structure plot of CSi for a fully relaxed ZB crystalline cell.

[0038] FIG. 11B is a band structure plot of CSi for a ZB crystalline cell strained to a Si (001) surface.

[0039] FIG. 11C is a band structure plot of CSi for a ZB crystalline cell strained to a Si (110) surface.

[0040] FIG. 11D is a band structure plot of CSi for a ZB crystalline cell strained to a Si (111) surface.

[0041] FIG. 12A is a band structure plot of CGe for a fully relaxed ZB crystalline cell.

[0042] FIG. 12B is a band structure plot of CGe for a ZB crystalline cell strained to a Si (001) surface.

[0043] FIG. 12C is a band structure plot of CGe for a ZB crystalline cell strained to a Si (110) surface.

[0044] FIG. 12D is a band structure plot of CGe for a ZB crystalline cell strained to a Si (111) surface.

[0045] FIG. 13A is a band structure plot of CSn for a fully relaxed ZB crystalline cell.

[0046] FIG. 13B is a band structure plot of CSn for a ZB crystalline cell strained to a Si (001) surface.

[0047] FIG. 13C is a band structure plot of CSn for a ZB crystalline cell strained to a Si (110) surface.

[0048] FIG. 13D is a band structure plot of CSn for a ZB crystalline cell strained to a Si (111) surface.

[0049] FIG. 14A is a band structure plot of CPb for a fully relaxed ZB crystalline cell.

[0050] FIG. 14B is a band structure plot of CPb for a ZB crystalline cell strained to a Si (001) surface.

[0051] FIG. 14C is a band structure plot of CPb for a ZB crystalline cell strained to a Si (110) surface.

[0052] FIG. 14D is a band structure plot of CPb for a ZB crystalline cell strained to a Si (111) surface.

[0053] FIG. 15A is a band structure plot of SiGe for a fully relaxed ZB crystalline cell.

[0054] FIG. 15B is a band structure plot of SiGe for a ZB crystalline cell strained to a Si (001) surface.

[0055] FIG. 15C is a band structure plot of SiGe for a ZB crystalline cell strained to a Si (110) surface.

[0056] FIG. 15D is a band structure plot of SiGe for a ZB crystalline cell strained to a Si (111) surface.

[0057] FIG. 16A is a band structure plot of SiSn for a fully relaxed ZB crystalline cell.P AT E N T Docket No. QS3101

[0058] FIG. 16B is a band structure plot of SiSn for a ZB crystalline cell strained to a Si (001) surface.

[0059] FIG. 16C is a band structure plot of SiSn for a ZB crystalline cell strained to a Si (110) surface.

[0060] FIG. 16D is a band structure plot of SiSn for a ZB crystalline cell strained to a Si (111) surface.

[0061] FIG. 17A is a band structure plot of SiPb for a fully relaxed ZB crystalline cell.

[0062] FIG. 17B is a band structure plot of SiPb for a ZB crystalline cell strained to a Si (001) surface.

[0063] FIG. 17C is a band structure plot of SiPb for a ZB crystalline cell strained to a Si (110) surface.

[0064] FIG. 17D is a band structure plot of SiPb for a ZB crystalline cell strained to a Si (111) surface.

[0065] FIG. 18A is a band structure plot of GeSn for a fully relaxed ZB crystalline cell.

[0066] FIG. 18B is a band structure plot of GeSn for a ZB crystalline cell strained to a Si (001) surface.

[0067] FIG. 18C is a band structure plot of GeSn for a ZB crystalline cell strained to a Si (110) surface.

[0068] FIG. 18D is a band structure plot of GeSn for a ZB crystalline cell strained to a Si (111) surface.

[0069] FIG. 19A is a band structure plot of GePb for a fully relaxed ZB crystalline cell.

[0070] FIG. 19B is a band structure plot of GePb for a ZB crystalline cell strained to a Si (001) surface.

[0071] FIG. 19C is a band structure plot of GePb for a ZB crystalline cell strained to a Si (110) surface.

[0072] FIG. 19D is a band structure plot of GePb for a ZB crystalline cell strained to a Si (111) surface.

[0073] FIG. 20A is a band structure plot of SnPb for a fully relaxed ZB crystalline cell.

[0074] FIG. 20B is a band structure plot of SnPb for a ZB crystalline cell strained to a Si (001) surface.

[0075] FIG. 20C is a band structure plot of SnPb for a ZB crystalline cell strained to a Si (110) surface.

[0076] FIG. 20D is a band structure plot of SnPb for a ZB crystalline cell strained to a Si (111) surface.

[0077] FIG. 21A is a band structure plot of CSi4 for a fully relaxed 5-atom tetrahedral crystalline cell.

[0078] FIG. 21B shows a band structure plot of CSi4 for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0079] FIG. 21C shows a band structure plot of CSi4 for a 5-atom tetrahedral crystalline cell strained to a Si (110) surface.

[0080] FIG. 21D shows a band structure plot of CSi4 for a 5-atom tetrahedral crystalline cell strained to a Si (111) surface.

[0081] FIG. 22A shows a band structure plot of CGe4 for a fully relaxed 5-atom tetrahedral crystalline cell.P AT E N T Docket No. QS3101

[0082] FIG. 22B shows a band structure plot of CGe4 for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0083] FIG. 22C shows a band structure plot of CGe4 for a 5-atom tetrahedral crystalline cell strained to a Si (110) surface.

[0084] FIG. 22D shows a band structure plot of CGe4 for a 5-atom tetrahedral crystalline cell strained to a Si (111) surface.

[0085] FIG. 23A shows a band structure plot of CSn4 for a fully relaxed 5-atom tetrahedral crystalline cell.

[0086] FIG. 23B shows a band structure plot of CSn4 for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0087] FIG. 23C shows a band structure plot of CSn4 for a 5-atom tetrahedral crystalline cell strained to a Si (110) surface.

[0088] FIG. 23D shows a band structure plot of CSn4 for a 5-atom tetrahedral crystalline cell strained to a Si (111) surface.

[0089] FIG. 24A shows a band structure plot of SiGe4 for a fully relaxed 5-atom tetrahedral crystalline cell.

[0090] FIG. 24B shows a band structure plot of SiGe4 for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0091] FIG. 24C shows a band structure plot of SiGe4 for a 5-atom tetrahedral crystalline cell strained to a Si (110) surface.

[0092] FIG. 24D shows a band structure plot of SiGe4 for a 5-atom tetrahedral crystalline cell strained to a Si (111) surface.

[0093] FIG. 25A shows a band structure plot of GeSi4 for a fully relaxed 5-atom tetrahedral crystalline cell.

[0094] FIG. 25B shows a band structure plot of GeSi4 for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0095] FIG. 25C shows a band structure plot of GeSi4 for a 5-atom tetrahedral crystalline cell strained to a Si (110) surface.

[0096] FIG. 25D shows a band structure plot of GeSi4 for a 5-atom tetrahedral crystalline cell strained to a Si (111) surface.P AT E N T Docket No. QS3101

[0097] FIG. 26A shows a band structure plot of SnSi4 for a fully relaxed 5-atom tetrahedral crystalline cell.

[0098] FIG. 26B shows a band structure plot of SnSi4 for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0099] FIG. 26C shows a band structure plot of SnSi4 for a 5-atom tetrahedral crystalline cell strained to a Si (110) surface.

[0100] FIG. 26D shows a band structure plot of SnSi4 for a 5-atom tetrahedral crystalline cell strained to a Si (111) surface.

[0101] FIG. 27A shows a band structure plot of PbSi4 for a fully relaxed 5-atom tetrahedral crystalline cell.

[0102] FIG. 27B shows a band structure plot of PbSi4 for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0103] FIG. 27C shows a band structure plot of PbSi4 for a 5-atom tetrahedral crystalline cell strained to a Si (110) surface.

[0104] FIG. 27D shows a band structure plot of PbSi4 for a 5-atom tetrahedral crystalline cell strained to a Si (111) surface.

[0105] FIG.28A shows a band structure plot of CSi3Ge for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0106] FIG.28B shows a band structure plot of CSi3Ge for a 5-atom tetrahedral crystalline cell strained to a Si (111) surface.

[0107] FIG. 29A shows a band structure plot of CSi2Ge2 for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0108] FIG. 29B shows a band structure plot of CSi2Ge2 for a 5-atom tetrahedral crystalline cell strained to a Si (111) surface.

[0109] FIG.30A shows a band structure plot of CSiGe3for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0110] FIG.30B shows a band structure plot of CSiGe3 for a 5-atom tetrahedral crystalline cell strained to a Si (111) surface.

[0111] FIG. 31 shows a band structure plot of CSisSn for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.P AT E N T Docket No. QS3101

[0112] FIG. 32 shows a band structure plot of CSi2Sn2 for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0113] FIG. 33 shows a band structure plot of CSiSn3 for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0114] FIG. 34 shows a band structure plot of CGe3Sn for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0115] FIG. 35 shows a band structure plot of CGe2Sn2 for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0116] FIG. 36 shows a band structure plot of CGeSn3 for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0117] FIG. 37A shows a band structure plot of CSi3Pb for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0118] FIG. 37B shows a band structure plot of CSi3Pb for a 5-atom tetrahedral crystalline cell strained to a Si (1 11) surface.

[0119] FIG. 38A shows a band structure plot of CGe3Pb for a 5-atom tetrahedral crystalline cell strained to a Si (001) surface.

[0120] FIG. 38B shows a band structure plot of CGe3Pb for a 5-atom tetrahedral crystalline cell strained to a Si (1 11) surface.

[0121] FIG. 39A shows a crystal structure constructed on top of a Si (00 1) surface, composed of a CSi QW made of a single ZB cell, with a Si QB made of 15 diamond cells. Brown color identifies C atoms, and blue color identifies Si atoms.

[0122] FIG. 39B shows a band structure plot of a crystalline cell strained to a Si (0 0 1) surface, composed of a CSi QW made of a single ZB cell, with a Si QB made of 15 diamond cells.

[0123] FIG. 40A shows a crystal structure constructed on top of a Si (00 1) surface, composed of a CGe QW made of a single ZB cell, with a Si QB made of 15 diamond cells. Brown color identifies C atoms, gray color identifies Ge atoms, and blue color identifies Si atoms.

[0124] FIG. 40B shows a band structure plot of a crystalline cell strained to a Si (0 0 1) surface, composed of a CGe QW made of a single ZB cell, with a Si QB made of 15 diamond cells.

[0125] FIG. 41A shows a crystal structure constructed on top of a Si (00 1) surface, composed of a CSn QW made of a single ZB cell, with a Si QB made of 15 diamond cells. Brown color identifies C atoms, orange color identifies Sn atoms, and blue color identifies Si atoms.P AT E N T Docket No. QS3101

[0126] FIG. 41B shows a band structure plot of a crystalline cell strained to a Si (0 0 1) surface, composed of a CSn QW made of a single ZB cell, with a Si QB made of 15 diamond cells.

[0127] FIG. 42A shows a crystal structure constructed on top of a Si (001) surface, composed of a CPb QW made of a single ZB cell, with a Si QB made of 15 diamond cells. Brown color identifies C atoms, black color identifies Pb atoms, and blue color identifies Si atoms.

[0128] FIG. 42B shows a band structure plot of a crystalline cell strained to a Si (0 0 1) surface, composed of a CPb QW made of a single ZB cell, with a Si QB made of 15 diamond cells.

[0129] FIG. 43A shows a crystal structure constructed on top of a Si (001) surface, composed of of a CSn QW made of two ZB cells, with a Si QB made of 15 diamond cells. Brown color identifies C atoms, orange color identifies Sn atoms, and blue color identifies Si atoms.

[0130] FIG. 43B shows a band structure plot of a crystalline cell strained to a Si (0 0 1) surface, composed of a CSn QW made of two ZB cells, with a Si QB made of 15 diamond cells.

[0131] FIG. 44A shows a crystal structure constructed on top of a Si (001) surface, composed of a QW made of two atomic planes of Ge, one atomic plane of C, and two atomic planes of Ge, with a Si QB made of 29 atomic planes. Brown color identifies C atoms, gray color identifies Ge atoms, and blue color identifies Si atoms.

[0132] FIG. 44B shows a band structure plot of a crystalline cell strained to a Si (0 0 1) surface, composed of a QW made of two atomic planes of Ge, one atomic plane of C, and two atomic planes of Ge, with a Si QB made of 29 atomic planes.

[0133] FIG. 45A shows a crystal structure constructed on top of a Si (001) surface, composed of a QW made of one atomic plane of Sn, one atomic plane of C, and one atomic plane of Sn, with a Si QB made of 29 atomic planes. Brown color identifies C atoms, orange color identifies Sn atoms, and blue color identifies Si atoms.

[0134] FIG. 45B shows a band structure plot of a crystalline cell strained to a Si (0 0 1) surface, composed of a QW made of one atomic plane of Sn, one atomic plane of C, and one atomic plane of Sn, with a Si QB made of 29 atomic planes.

[0135] FIG. 46A shows a crystal structure constructed on top of a Si (001) surface, composed of a QW made of one atomic plane of C, one atomic plane of Sn, and one atomic plane of C, with a Si QB made of 29 atomic planes. Brown color identifies C atoms, orange color identifies Sn atoms, and blue color identifies Si atoms.P AT E N T Docket No. QS3101

[0136] FIG. 46B shows a band structure plot of a crystalline cell strained to a Si (0 0 1) surface, composed of a QW made of one atomic plane of C, one atomic plane of Sn, and one atomic plane of C, with a Si QB made of 29 atomic planes.

[0137] FIG. 47A shows a crystal structure constructed on top of a Si (001) surface, of the cell for the aperiodic or quasiperiodic SL constructed following the Cantor series of order N=3, using ZB cells of SiGe and Zinc-ZB cells of PbC. Brown color identifies C atoms, black color identifies Pb atoms, gray color identifies Ge atoms, and blue color identifies Si atoms.

[0138] FIG. 47B shows a band structure plot of a crystalline cell strained to a Si (001) surface, of the cell for the aperiodic or quasiperiodic SL constructed following the Cantor series of order N=3, using ZB cells of SiGe and Zinc-ZB cells of PbC.

[0139] FIG. 48A shows a crystal structure constructed on top of a Si (001) surface, of the cell for the aperiodic or quasiperiodic SL constructed following the Fibonacci series of order N=3, using ZB cells of GeC and diamond cells of Si to form two identical GeC Ws having two Si QBs of different thicknesses. Brown color identifies C atoms, gray color identifies Ge atoms, and blue color identifies Si atoms.

[0140] FIG. 48B shows a band structure plot of a crystalline cell strained to a Si (001) surface, of the cell for the aperiodic or quasiperiodic SL constructed following the Fibonacci series of order N=3, using ZB cells of GeC and diamond cells of Si to form two identical GeC QWs having two Si QBs of different thicknesses.

[0141] FIG. 49A shows a crystal structure constructed on top of a Si (001) surface, of the cell for the aperiodic or quasiperiodic SL constructed following the Rudin-Shapiro series of order N=3, using ZB cells of SiGe and ZB cells of PbC. Brown color identifies C atoms, black color identifies Pb atoms, gray color identifies Ge atoms, and blue color identifies Si atoms.

[0142] FIG. 49B shows a band structure plot of a crystalline cell strained to a Si (001) surface, of the cell for the aperiodic or quasiperiodic SL constructed following the Rudin-Shapiro series of order N=3, using ZB cells of SiGe and ZB cells of PbC.

[0143] FIG. 50A shows a crystal structure constructed on top of a Si (001) surface, of the cell for the aperiodic or quasiperiodic SL constructed following the Thue-Morse series of order N=4, using ZB cells of SiGe and ZB cells of PbC. Brown color identifies C atoms, black color identifies Pb atoms, gray color identifies Ge atoms, and blue color identifies Si atoms.

[0144] FIG. 50B shows a band structure plot of a crystalline cell strained to a Si (001) surface, of the cell for the aperiodic or quasiperiodic SL constructed following the Thue-Morse series of order N=4, using ZB cells of SiGe and ZB cells of PbC.P AT E N T Docket No. QS3101

[0145] FIG. 51A shows 16-atom crystalline cell strained to a Si (001) surface, comprising 4 C atoms and 12 Sn atoms describing the crystal SneC2, having C-C bonds.

[0146] FIG. 51B shows a band structure plot of the 16-atom crystalline cell strained to a Si (0 0 1) surface, comprising 4 C atoms and 12 Sn atoms describing the crystal SneCz, having C-C bonds.

[0147] FIG. 52 - Table 6.

[0148] FIG. 53 shows an exemplary crystalline cell to implement two QWs, each consisting of a single ZB cell (for example GeC), separated by an odd number of atomic planes of the Si QBs, such that the angle of the bonds between the two elements of the ZB cell are rotated by 90 degrees from one ZB cell to the other. Brown color identifies C atoms, gray color identifies Ge atoms, and blue color identifies Si atoms.

[0149] FIG. 54A shows an exemplary crystalline cell to implement a QW, consisting of a single ZB cell (for example GeC), separated by an even number of atomic planes of the Si QBs from other identical QWs, such that the angle of the bonds between the two elements of the ZB cell are identical from one ZB cell to the other. Brown color identifies C atoms, gray color identifies Ge atoms, and blue color identifies Si atoms.

[0150] FIG. 54B shows an exemplary crystalline cell to implement a QW, similar to that of FIG. 54A, but having the angle of the bonds between the two elements of the ZB cell being identical from one ZB cell to the other, but rotated by 90 degrees from the ZB cells of FIG. 54A. Brown color identifies C atoms, gray color identifies Ge atoms, and blue color identifies Si atoms.

[0151] FIG. 55 is a flowchart illustrating a process for fabricating a semiconductor device, according to some embodiments of the disclosed technologies.Detailed Description

[0152] The most commonly used epitaxial group-IV alloy is silicon-germanium (SiGe or GeSi), with varying percentages of Ge in the films, strained to the Si (001) surface. Because Ge is highly immiscible with Si, it is possible to form SiGe random alloys with a continuous wide range of Ge percentage. This is typically done using separate precursors for Si and for Ge, for example Silane (SiFU), or Disilane (Si2He) for Si, and Germane (GeH₄) or Digermane (Ge₂H₆) for Ge. The epitaxial growth of SiGe films proceeds by co-flowing the Si-precursor and the Ge-precursor, in which the flow ratios of each precursor are a key factor determining the percentage of Ge in the epitaxial layers.

[0153] Within a given volume of the SiGe random alloy, the overall number of Ge atoms can be very well controlled, but within that volume the spatial distribution of the Ge atoms is completely random. This is true even for a Sio.sGeo.s composition, which conceivably could form a perfectly ordered alloy,P AT E N T Docket No. QS3101 in which each Si atom would be bonded only to Ge atoms, and conversely each Ge atom would be bonded only to Si atoms, thereby forming a Zinc-Blende (ZB) cell.

[0154] For Sio.sGeo.s layers epitaxially grown on (001) or (111) surfaces, there is an alternance of an atomic plane populated only with Si atoms, with an atomic plane populated only with Ge atoms. For epitaxial growth on (110) surfaces, each atomic plane would have the exact same number of Si and Ge atoms.

[0155] In such a case the SiGe-ZB material would be a group-IV compound semiconductor, an expression commonly used for Silicon Carbide (SiC), in which each Si atom is bonded only to C atoms, and each C atom is bonded only to Si atoms.

[0156] The typical epitaxial growth of Silicon Carbide also uses separate precursors for Si and C, but the chemistry is such that there are no Si-Si, nor C-C bonds, and only Si-C bonds are formed. For epitaxial growth on a face centered cubic (001) surface this means that Si atoms and C atoms populate alternate atomic planes, with the distance between these atomic planes being % of the lattice constant.

[0157] 1. On Epitaxial Layers Strained to Silicon with High Carbon Percentage

[0158] Until 2016, prior art in the epitaxial growth of Silicon and / or SiGe layers with Carbon, shows that it is very difficult to incorporate carbon substitutionally beyond 3%, mostly due to the very low immiscibility of C in Si, Ge, and Sn.

[0159] Experimental results published in 2016, describe a methodology, using suitable CVD precursors and epitaxial growth conditions, demonstrating the growth of SiC delta layers strained to a crystalline Ge relaxed buffer layer: Y. Yamamoto, N. Ueno, M. Sakuraba, J. Murota, A. Mai, B. Tillack, " C and Si delta doping in Ge by CH₃SiH₃ using reduced pressure chemical vapor deposition", Thin Solid Films Vol. 602 (3), 24-28 (2016), DOI: 10.1016 / j.tsf.2015.09.046.

[0160] The work from Yamamoto et al., using the precursor CH₃SiH₃ to fabricate SiC layers strained to a relaxed Ge layer, provides guidance to fabricate GeC, SnC and PbC, layers strained to Si, using similar precursors in which Si is replaced by Ge, or Sn, or Pb, i.e., CH₃GeH₃, CH₃SnH₃, CH₃PbH₃. An ab-initio study of these precursors was published in 1992: P. v. R. Schleyer, M. Kaupp, F. Hampel, M. Bremer, and K. Mislow, " Relationships in the rotational barriers of all Group 14 ethane congeners H3X-YH3 (X, Y = C, Si, Ge, Sn, Pb). Comparisons of ab initio pseudopotential and all-electron results", Journal of the American Chemical Society, 114 (17), 6791-6797 (1992), DOI: 10.1021 / ja00043a026.

[0161] It should be kept in mind that in general, the engineering of sophisticated heterojunctions with sharp composition profiles and interfaces, benefits from epitaxial growth at lower temperatures,P AT E N T Docket No. QS3101 below 500 °C, and possibly even below 350 °C. Since critical thicknesses depend exponentially on temperature, the epitaxial growth at lower temperatures significantly increases the critical thickness of the compositions discussed in this disclosure.

[0162] 2. Ordered Alloys with Zinc-Blende Cells

[0163] 0ne way to form ordered alloys, and ZB cells of compound semiconductors, is to perform pulsed deposition of atomic plane by atomic plane, alternating the injection of chemical precursors, with the goal of alternating one atomic plane of Si and an atomic plane of Ge. However, this methodology is perceived to be very time-consuming and therefore inefficient and unsuitable for high volume manufacturing.[00164JA perfectly ordered crystal can be made through the sequential deposition of ZB cells, with the two atoms of the ZB cell being already bonded in the chemical precursor, and with that bonding remaining intact upon adsorption into the epitaxial growth front of the solid film. The following reference provides examples of precursors that can be used to sequentially deposit ZB cells, in this case composed of Si and Ge, but that can be also extended to C, Sn and Pb: J. B. Tice, A. V. G. Chizmeshya, R. Roucka, J. Tolle, B. R. Cherry, and J. Kouvetakis, " ClnH6-nSiGe Compounds for CMOS Compatible Semiconductor Applications: Synthesis and Fundamental Studies", J. Am. Chem. Soc. 129 (25), 7950-7960 (2007), DOI: 10.1021 / j a 0713680. Examples of ZB cell compositions and respectiveprecursors are listed in Table 1A, in FIG. 1A.

[0165] It should be noted that in certain cases the elements bonded with a halogen (e.g., Cl) and H could be swapped, and that in certain cases H could be replaced by Deuterium (D). It is also important to note that a Hydrogen (or Deuterium)-terminated surface, is likely to attract first the portion of a precursor molecule that is terminated by halogen atoms. Conversely, a halogen-terminated surface, is likely to attract first the portion of a precursor molecule that is terminated by Hydrogen (or Deuterium) atoms. In other cases the molecule backbone, X-Y, where X and Y are group-IV elements, could be surrounded by just Hydrogens and / or Deuteriums, or the backbone X-Y could be surrounded just by one or more species of Halogens.

[0166] However, this "selectivity" for the initiation of precursor adsorption, and therefore ordered stacking of chemical species, does not exist for precursor molecules of the kind H3X-YH3, or Ha₃X-YHa₃. where X, Y = C, Si, Ge, Sn, Pb, and Ha is a halogen. The choice of precursors with different bonding arrangements in the precursor molecule for H (or D) and halogens (F, or Cl, or Br,...) enables different preferential stacking sequences and therefore ordered alloys with different composition profiles. Other precursors for PbC, with more than one bond between Pb and C, may also be useful.P AT E N T Docket No. QS3101

[0167] For example, flowing Cl₃Ge-SiH₃, should result in a sequence of adsorptions as follows, Si-substrate-surface (chlorine terminated) - FhSi-GeCh - H₃Si-GeCl₃ - H₃Si-GeCl₃ - H₃Si-GeCl₃, which in turn should result in a solid growth front that progresses by stacking Si-Ge ZB cells as follows, Si-substrate-surface-(Si-Ge)-(Si-Ge)-(Si-Ge)-(Si-Ge), i.e., a stacking of atomic planes with only one chemical species per atomic plane.

[0168] For a Si-substrate-surface (hydrogen terminated), the sequence of adsorptions would be as follows: Si-substrate-surface - Cl₃Ge-SiH₃ - Cl₃Ge-SiH₃ - Cl₃Ge-SiH₃ - Cl₃Ge-SiH₃, which in turn should result in a solid growth front that progresses by stacking Ge-Si ZB cells as follows, Si-substrate-surface-(Ge-Si)-(Ge-Si)-(Ge-Si)-(Ge-Si), i.e., reversing the stacking order of the atomic planes populated with Si and those populated with Ge.

[0169] 3. Ordered Alloys with 5-Atom Tetrahedral Cells

[0170] A perfectly ordered crystal can also be made through the sequential deposition of 5-atom tetrahedral cells, with the five atoms of the cell having already the desired bonding arrangement in the chemical precursor, and with that bonding arrangement remaining intact upon adsorption into the epitaxial growth front of the solid film. Examples of 5-atom tetrahedral cell compositions and respective precursors are listed in Table IB, in FIG. IB.

[0171] The following reference provides examples of precursors (hydrides) that can be used to sequentially deposit 5-atom tetrahedral cells, in this case composed of Si and Ge, but that can be also extended to other group-IV elements: C. J. Ritter, C. Hu, A. V. G. Chizmeshya, J. Tolle, D. Klewer, I. S. T. Tsong, J. Kouvetakis, " Synthesis and Fundamental Studies of (H3Ge)xSiH4-xMolecules: Precursors to Semiconductor Hetero- and Nanostructures on Si", J. Am. Chem. Soc. 2005, 127, 9855-9864, DOI:10.1021 / ja051411o.

[0172] The following reference provides examples of precursors (chlorides) that can be used to sequentially deposit 5-atom tetrahedral cells, that include C, Si, Ge, but that can be also extended to other group-IV elements: J. Teichmann, C. Kunkel, I. Georg, M. Moxter, T. Santowski, M. Bolte, H.-W. Lerner, S. Bade, M. Wagner, " Trisftrich lorosilyl)tetrelide Anions and a Comparative Study of Their Donor Qualities" Chem. Eur. J. 2019, 25, 2740, DOI: 10.1002 / chem.201806298.

[0173] Examples of such precursors are (H₃Ge)₄Si, (HaSi^Ge, (CfeSihGe, and the crystal compositions that each deterministically form are Ge₄Si and Si4Ge, respectively, through the reactions (H₃Ge)₄Si (gas) -> Ge₄Si (film) + 6H2 (gas), (H₃Si)₄Ge (gas) -> Si4Ge (film) + 6H2 (gas), or (Cl₃Si)₄Ge (gas) -> Si4Ge (film) + 6CI2 (gas), or maybe 12HCI instead of 6CI2, because of the carrier gas H2 typically present in the CVD reactor.P AT E N T Docket No. QS3101

[0174] Ge4Si is an ordered alloy in which each Si atom is surrounded by four 4 nearest neighbors Ge atoms, and in which necessarily the Si atoms are third nearest neighbors of each other. Si4Ge has the reverse situation: an ordered alloy in which each Ge atom is surrounded by four 4 nearest neighbors Si atoms, and in which necessarily the Ge atoms are third nearest neighbors of each other. Other possible variations of precursors include (XaY^Z, in which X can be hydrogen, deuterium or a halide, and Y and Z can both be C, Si, Ge, Sn, Pb.

[0175] 4. Quantum-Wells + Quantum-Barriers and Superlattices

[0176] The stacking of ZB cells can be used to epitaxially grow QWs and SLs of the form (X-Y)m-(Q-Z)n, where X, Y = C, Si, Ge, Sn, Pb, and Q, Z= C, Si, Ge, Sn, Pb, and in which "m" and "n" are the number of ZB cells for each ZB cell composition. If X=Y or Q=Z, then the respective ZB cell becomes a diamond cell. The key difference between QWs and SLs are the thickness of the QB layers, which are much thicker for QWs than for SLs, thereby decoupling the wavefunctions of carriers in adjacent QWs, and forming discrete quantized energy levels instead of energy minibands.

[0177] If the epitaxial growth of a QW or a SL layer stack combines ZB cells and 5-atom tetrahedral cells in the same layer, then that layer is a random alloy, and whenever it is repeated it may not have the exact same composition and / or atomic ordering (even if it had the same stoichiometry).

[0178] On the other hand, if the epitaxial growth of a QW or a SL layer stack the incorporates ZB cells and 5-atom tetrahedral cells in different layers, and possibly other layers having a single chemical species, then it is possible to fabricate an entire layer stack that has a deterministic atomic ordering of all chemical species incorporated in it. The combination of ZB cells and 5-atom tetrahedral cells in different layers can also be used for strain engineering of the overall superlattice layer stack.

[0179] In Table 3A in FIG. 3A, and Table 3B in FIG. 3B, the column named " Vertical Ratio", refers to the ratio of heights (i.e., ratio of lattice constant in the direction of epitaxial pseudomorphic growth) of a material with respect to Si. The Vertical Ratio is < 1 for tensile strain, and > 1 for compressive strain. Alternating materials with Vertical Ratios larger and smaller than 1, enables layer stacks with Vertical Ratios closer to 1, that is, enables strain-balancing of an epitaxial layer stack, thereby exponentially increasing the critical thickness.

[0180] For example, Ge4C, strained to Si (0 0 1), has an indirect band-gap of 0.385 eV. It is also possible to make superlattices with deterministic C, Ge, and Si percentage and atomic positions: (Ge4C)m-(Ge4Si)n, or (Ge4C)m-(SiGe)n, or (Ge4C)m-(Ge5)n.

[0181] Another example is Si4Sn, strained to Si (0 0 1), which has an indirect band-gap of 0.640 eV. With precursors, such as (H₃Si)₄Sn it is possible to engineer QWs and SLs such as (Ge4C)m-(Sn4C)n, orP AT E N T Docket No. QS3101 (Ge4C)m-(Si4Sn)n. According to the data in Table 3B, in FIG. 3B, the vertical aspect ratios of Ge4C and Sn4C, are respectively, 0.9156 and 1.1142, which nearly balance each other, resulting in a combined vertical aspect ratio of 1.0149. Even closer matches to silicon, are obtained for (Ge4C)3-(Sn4C)2, (ratio = 0.9950) and (Ge4C)4-(Sn4C)3, (ratio = 1.0007).

[0182] According to the data in Table 3B, in FIG. 3B, the vertical aspect ratios of Ge4C and Si₄Sn, are respectively, 0.9156 and 1.0618, which nearly balance each other, resulting in a combined vertical aspect ratio of 0.9887, and layer stacks with vertical aspect ratios very close to unity include: (Ge₄C)₂-(Si₄Sn)₃, (ratio = 1.00332) and (Ge₄C)₃-(Si₄Sn)₄, (ratio = 0.99914).

[0183] The precursors listed in the Table 1A, in FIG. 1A and table IB, in FIG. IB are just examples, and several variations in the number and locations of H (or D) and a halogen, can also produce the desired effect: the bond between the elements that exists in the precursor, will remain unbroken after adsorption into the epitaxial growth front, and will be part of the solid film.

[0184] This approach forces the incorporated atoms into deterministic relative positions, thereby forming a group-IV ordered alloy, or QWs and SLs having ordered alloys as the QW and / or as the QBs. Conceptually this is true independently from the crystallographic orientation of the surface on which the epitaxial growth is performed.

[0185] 5. On Ordered Materials: Alloys, QWs, SLs

[0186] The perfect periodicity of the location of the atoms in the crystalline lattice of the ordered alloy, QW, or periodic superlattice (composed of ZB cells and / or 5-atom tetrahedral cells), means that the periodic part of the electron's wave function, the Bloch function, incorporates that perfect periodicity of the different chemical species in their respective sites, and therefore there is no reason for "alloy scattering".

[0187] Consequently an ordered-alloy / compound-semiconductor will have higher mobility than the compositionally / stoichiometrically equivalent random alloy, and devices made with an ordered-alloy / compound-semiconductor will have higher performance than devices made with random alloys. This is true for any ordered-alloy / compound-semiconductor formed by stacking any of the ZB cells listed in the Table 1A, in FIG. 1A, and any of the 5-atom tetrahedral cells listed in Table IB, in FIG. IB, incorporating any of the group-IV elements.

[0188] Also, the precursors listed in Table 1A, in FIG. 1A, may have each of the two group-IV chemical species consisting of a single, pre-defined, isotope. Likewise, the precursors listed in Table IB FIG. IB, may have each of the group-IV chemical species (which may be more than two) consisting of a single,P AT E N T Docket No. QS3101 pre-defined, isotope. Multiple versions of the chemically identical precursor may exist with permutations of the isotopes for each species.

[0189] Such isotopically-engineered precursors would be very useful to engineer multiple phononic band structures, with the same chemical composition, and therefore with the same (or nearly identical) electronic band structure. Physical parameters such as electron-phonon coupling, and the macroscopic properties that it affects, could be significantly changed or engineered by changing the phonon band structure.

[0190] 6. On Resilience to Disorder

[0191] There is one important difference between using the precursors for ZB cells and the precursors for 5-atom tetrahedral cells. With the latter the atom at the center of the 5-atom tetrahedral structure cannot form bonds with any other atoms, and therefore there is no risk of forming anti-phase domains, a possibility that exists for ZB cells using the precursors in Table 1A FIG.1A.

[0192] Under ideal surface and growth conditions, with precursors such as Cl₃Ge-SiH₃, there are no Si-Si and no Ge-Ge bonds in ZB cells, but the presence of terraces on the substrate on which the epitaxial growth takes place may lead to Si-Si and Ge-Ge bonds, thereby forming anti-phase domains or boundaries. This may not be critical for SiGe materials, but it can be for the epitaxial growth of CSi, or CGe, or CSn, or CPb, in which C-C bonds can cause dramatic changes to the band structure, and therefore to the overall optoelectronic properties. Anti-phase domains or boundaries are also known to be one of the critical problems for the growth of lll-V compound semiconductors on silicon substrates.

[0193] In typical silicon substrates (i.e., wafers), the surface of typical wafers have atomic steps and terraces. Likewise, the surface of "active areas", i.e., silicon surfaces surrounded by isolation (dielectric materials) structures, such as those created by Shallow Trench Isolation (STI), typically have also multiple atomic steps and terraces.

[0194] The existence of atomic steps and terraces on the silicon surface, on which the epitaxial growth will take place, can be a source of defects (anti-phase domains or boundaries) and variability in surface conditions that are undesirable. These can cause variations in the potential that can affect charge carriers when traveling along directions, parallel and perpendicular to the substrate. Also, different numbers of steps and sizes of terraces of separate active areas in the same wafer, or from wafer to wafer, may determine different incubation times for epitaxial growth, and therefore may produce differences in layer thicknesses, for epitaxial films that should be nominally identical.P AT E N T Docket No. QS3101

[0195] In order to minimize perturbation to the "perfect ordering" of the desired chemical and / or isotopic compositions and atomic placements within the epitaxial layers, it may be desirable to perform the epitaxial growth on mono-terrace silicon surfaces, thereby avoiding the potential problems posed by atomic steps and terraces on the surface on which the epitaxial growth will take place. The creation of mono-terrace surfaces from surfaces having multiple atomic steps and terraces has been demonstrated in the late 1990's, and the following reference provides a method to create mono-terrace surfaces: D. Lee and J. Blakely, " Formation and stability of large step-free areas on Si (001) and Si (111)", Surface science 445 (1), 32-40 (2000), DOI: 10.1016 / S0039-6028(99)01034-1.

[0196] 0n the other hand, 5-atom tetrahedral cells, through their precursors, may provide process robustness against a variety of factors that could create defects, or somehow impact negatively the epitaxial growth of ordered alloys and superlattices constructed by stacking ordered alloys, as well as random alloys and superlattices constructed by stacking random alloys, QWs, etc. The 5-atom tetrahedral cells, through their precursors, may also enable the fabrication of material compositions that would otherwise be very difficult, or impossible, to grow with conventional precursors, and even with the specialty precursors for ZB cells.

[0197] 5-atom tetrahedral cells enable an unique situation, which cannot be guaranteed by any other approach, and which is best explained through an example, without loss of generality. The layer-by-layer epitaxial growth, alternating the (H₃Ge)₄C and (H₃Si)₄C precursors, should lead to a stack of layers consisting of Ge4C alternated with Si4C. The average composition of an even number of pairs of Ge4C and Si4C is 50% / 50%.

[0198] This configuration has the advantage of being immune to presence of terraces on the substrate surface on which the epitaxial growth is performed, i.e., neither C-C bonds can ever be formed, regardless of the number of terrace steps, or growth along edges or corners in patterned substrates, where boundaries between single crystalline material and poly-crystalline material (formed on a dielectric material such as SiO2or Si₃N₄) might exist.

[0199] 7. New Methodology for a Wide Range of Compositions

[0200] The engineering of band structures and band-gaps, can have a wider range of variation when the aforementioned precursors for epitaxially depositing ZB cells are co-flowed with single-element precursors such as Silane (SiH₄), Disilane (Si₂H₆), Dichlorosilane (H2SiCI2), for Si, and / or Germane (GeH₄), or Digermane (Ge₂H₆), or Germanium Tetrachloride (GeCk) for Ge, and / or Tin Tetrachloride (SnCl₄), and / or Tin Tetrabromide (SnBr₄) for Sn.

[0201] Naturally the co-flow of these types of precursors with the precursors that enable ZB cells will no longer produce ordered alloys, but will allow for wider range, and an almost continuous variation,P AT E N T Docket No. QS3101 of alloy compositions. Consequently, through the fine-tuning of alloy composition, there will be an increased granularity for band structure engineering of alloys, and / or QWs, and / or SLs.

[0202] The new approach to fabricating carbon-containing random alloys with a wide range of carbon concentrations, up to 50%, is novel and a key enabler to reaching high overall carbon content in an epitaxial layer, in a range from 0% to 50%, with a continuous variation of concentrations. This can be achieved by co-flowing a precursor that by itself can form layers with 50% Carbon (i.e., ZB cells with Carbon), with elemental precursors for the other chemical species in the ZB cell: Si, or Ge, or Sn, or Pb. Evidently, the critical thickness of the single-crystal layer will be determined by the composition.

[0203] It should be understood that this co-flow does not imply a continuous co-flow, and could be a pulsed co-flow to form delta-layers with carbon content between 0% and 50%. This can be accomplished using the growth methodology of Yamamoto et al, or other methodologies that enable the adsorption of the C-X (X= Si, or Ge, or Sn, or Pb) molecule and incorporate its stoichiometry in the epitaxial growth front. Without such methodologies, the incorporation of Carbon leads to low substitutional concentrations (typically < 3%), even when using a precursor molecule such as SiH₃CH₃.

[0204] When 5-atom tetrahedral cells (X4Y), with just 2 chemical species, are admixed with ZB cells with the same 2 chemical species (XY), it is possible to create alloys with ranges for X from 50% to 80%, or conversely for Y, from 20% to 50%. Naturally the different compositional ranges can have equally wide ranges of tensile or compressive strain, and thus can be used for strain engineering. Combining ZB cells with 5-atom tetrahedral cells having more than 2 chemical species opens another parameter space for the engineering of alloy composition, strain, optoelectronic and phonic properties.

[0205] For example, co-flowing (H₃Ge)₄Si with SiH₄ or Si₂H₆, makes it possible to deposit a random alloy with a continuous arbitrary Silicon percentage from 20% to 100%, or conversely a Germanium percentage from 80% to 0%. Co-flowing (H₃Si)₄Ge with SiH4or Si₂H₆, makes it possible to deposit a random alloy with a continuous arbitrary Silicon percentage from 80% to 100%, or conversely a Germanium percentage from 20% to 0%.

[0206] Co- flowing (H₃Ge)₄Si with GeH4or GeCl₄, makes it possible to deposit a random alloy with a continuous arbitrary Silicon percentage from 20% to 0%, or conversely a Germanium percentage from 80% to 100%. Co-flowing (H3Si)4Ge with GeH4or GeCl₄, makes it possible to deposit a random alloy with a continuous arbitrary Silicon percentage from 80% to 0%, or conversely a Germanium percentage from 20% to 100%.

[0207] There is a scenario in which co-flowing two different 5-atom tetrahedral precursors could lead to the formation of an ordered alloy with an overall chemical composition that would be the averageP AT E N T Docket No. QS3101 of the two precursors. This scenario requires one of the 5-atom tetrahedral precursor to be H (or D) terminated and the other 5-atom tetrahedral precursor to be halogen terminated. This may allow the co-flow of both precursors such that the adsorption of any molecule takes place only by bonding with dissimilar molecules.

[0208] An example for this scenario would be (Cl₃Ge)₄Si and (H₃Si)₄Ge, in which under suitable growth conditions, namely pressure, temperature and background carrier gas, the epitaxial growth would proceed only through the following reaction (C Ge^Si (gas) + (H₃Si)₄Ge (gas)(Ge4Si + Si4Ge) (film) + 12HCI (gas). In this case, an isotropic ordered alloy could be grown. This may not be critical for SiGe materials, but can be critical for Carbon containing materials (ordered and random alloys, QWs, and SLs).

[0209] There is no scientific literature describing such an approach to incorporate such high levels carbon in random alloys, and to vary the content over such wide ranges. High carbon content is required to achieve the novel crystal structures described above, and the novel physical properties described below.

[0210] 8. Electronic Band Structures

[0211] Density Functional Theory (DFT) studies of some of the ZB cells in Table 1A, in FIG. 1A, have been published, as exemplified by the following references: S. Q. Wang and H. Q. Ye, " Plane-wave pseudopotential study on mechanical and electronic properties for IV and lll-V crystalline phases with zinc-blende structure", Physical Review B 66, 235111 (2002), DOI: 10.1103 / PhysRevB.66.235111; N. Hammou, A. Zaoui, and M. Ferhat, " Revisiting Stabilities of Cubic Zincblende IV-IV Materials From Density Functional Theory", Phys. Status Solidi C 2017, 14, 1700226, DOI: 10.1002 / pssc.20170J. Ziembicki, P. Scharoch, M. P. Polak, M. Wisniewski, R. Kudrawiec; " Electronic and structural properties of group IV materials and their polytypes", J. Appl. Phys. 21 October 2024; 136 (15): 155702, DOI: 10.1063 / 5.0024832. The naming of the ZB cells in this disclosure incorporates the nomenclature for the ZB cells used in the reference above by J. Ziembicki et al.

[0212] DFT studies of some of the 5-atom tetrahedral cells in Table IB, in FIG. IB, have been published, as exemplified by the following reference:: P. Zhang, V. H. Crespi, E. Chang, S. G. Louie, and M. L. Cohen, " Theory of metastable group-IV alloys formed from CVD precursors", Phys. Rev. B 64, 235201, DOI: 10.1103 / PhysRevB.64.235201.

[0213] It must be noted that the structural optimizations performed in all references listed above were for the "natural" lattice parameters of each cell, and almost all the cells simulated do not have a substrate with a perfect lattice match to grow defect-free crystalline layers with thicknesses useful to fabricate devices. FIGs. 6 to 51, show the band structure plots along a k-path that includes theP AT E N T Docket No. QS3101 entire Brillouin Zone, which includes several equivalent k-points that remain equivalent for fully relaxed structures in 3D, but which may not be equivalent when the crystalline cells are under tensile or compressive strain, to silicon's 3 main crystallographic orientations: (001), (110), and (111).

[0214] FIGs. 6 to 27, show the band structures of the diamond and ZB cells.

[0215] FIGs. 28 to 38, show the band structures of 5-atom tetrahedral cells.

[0216] FIGs. 39 to 46 show the band structures of various QWs compositions and Si QBs, strained to Si (001) surfaces.

[0217] FIGs.47 to 50 show the band structures of a few aperiodic / quasiperiodic SLs strained to Si (0 01) surfaces.

[0218] FIGs. 51A, 51B show the crystal structure and band structure, respectively of SneC2, strained to Si (001), having Carbon-Carbon bonds.

[0219] FIG.52 shows Table 6.

[0220] FIG.53 shows an exemplary crystalline cell to implement two QWs, each consisting of a single ZB cell (for example GeC), separated by an odd number of atomic planes of the Si QBs, such that the angle of the bonds between the two elements of the ZB cell are rotated by 90 degrees from one ZB cell to the other. Brown color identifies C atoms, gray color identifies Ge atoms, and blue color identifies Si atoms.

[0221] FIGs.54A shows an exemplary crystalline cell to implement a QW, consisting of a single ZB cell (for example GeC), separated by an even number of atomic planes of the Si QBs from other identical QWs, such that the angle of the bonds between the two elements of the ZB cell are identical from one ZB cell to the other. Brown color identifies C atoms, gray color identifies Ge atoms, and blue color identifies Si atoms.

[0222] FIG. 54B shows an exemplary crystalline cell to implement a QW, similar to that of FIG. 54A, but having the angle of the bonds between the two elements of the ZB cell being identical from one ZB cell to the other, but rotated by 90 degrees from the ZB cells of FIG. 54A. Brown color identifies C atoms, gray color identifies Ge atoms, and blue color identifies Si atoms.

[0223] It is also very important to note that in the previous publications listed above that use pseudopotentials, the DFT simulations results for materials in which there is at least one Tin-Carbon bond, for example Tin Carbide (SnC or CSn), the pseudo-potentials for Sn did not include 3d orbitals, which are relevant when Tin is bonded to Carbon. The results in Table 2A in FIG. 2A, and Table 3A in FIG.3A, for CSn, were obtained with a pseudo-potential for Sn that includes the 3d orbitals. For previous DFT simulations of SnC (or CSn) ZB cells, only those performed with all-electron codes present reliableP AT E N T Docket No. QS3101 results, which is the case for the above referenced work of J. Ziembicki et al. The DFT results included in the present disclosure were obtained with the open source Plane-Wave Pseudo-Potential code cpw2000 (J. L. Martins et al., cpw2000, URL https: / / github.com / jim785 The pseudopotentials are of the Troullier-Martins type, and the pseudo-potential for Sn includes the 3d orbitals.

[0224] The foregoing comments about the DFT simulations, regarding the lack of inclusion of Tin's 3d orbitals, and the band structure calculations being performed for cells without the constraint of pseudomorphic compliance with silicon's lattice constant, are also true about the DFT simulations of 5-atom tetrahedral cells in the reference given above.

[0225] From a practical high volume manufacturing perspective, integration with CMOS technology favors the epitaxial pseudomorphic growth of the ZB cells and 5-atom tetrahedral cells, on silicon (00 1) substrates. Naturally, the band structures for the fully relaxed crystalline cells and for crystalline cells strained to Si substrates, can be radically different. Also, the band structures for strained crystalline cells can also be radically different for different Si surface orientations.

[0226] Although Lead Carbide (PbC or CPb) does not form naturally, it is possible, indeed likely, that it can be synthesized under non-equilibrium thermodynamic conditions, for example by CVD with a chemical precursor that has at least one Pb-C bond. Given PbC's fairly small lattice constant mismatch with respect to silicon, shown in Table 2A in FIG.2A, and Table 3A in FIG.3A, the constraint of epitaxial pseudomorphic growth might help its formation and subsequent stability.

[0227] The following publication suggests that PbC should be stable in ambient conditions: H. Munoz, J. E. Antonio, J. M. Cervantes, J. L. Rosas-Huerta, E. Carvajal and R. Escamilla, " First-principles study of the effect of pressure on the physical properties of PbC", Mater. Res. Express 10 (2023) 055601, DOI:10.1088 / 2053- 1591 / acd323.

[0228] It is well known that structural optimization with the Local Density Approximation (LDA) exchange and correlation potential for group-IV materials, results in the underestimation of experimental lattice constants in the range of 1% to 1.5%. In some cases there are significant differences between the band structure calculations for LDA relaxation and experimental lattice parameters.

[0229] The lattice parameters presented in Table 2A in FIG. 2A, and Table 2B in FIG. 2B, were obtained with a Valence Force Field (VFF) calibrated by experimental data (when available) and by the lattice parameters calculated using ELK (https: / / elk.sourceforge.io / anopen source all-electron fullpotential linearized augmented-plane wave (FP-LAPW) code, together with the r2-SCAN exchange and correlation potential, available through the open source library " Libxc" (https: / / libxc.gitlab.io). The VFF relaxation code is part of the above referenced open source cpw2000 package.P AT E N T Docket No. QS3101

[0230] The data in Table 2A is for the fully relaxed (in all directions, to their natural lattice parameters) ZB cells, using the lattice parameters produced by the VFF relaxation calibrated by experimental data and ELK+r2SCAN relaxation. Table 2B in FIG. 2B, has the data for the fully relaxed (in all directions, to their natural lattice parameters) 5-atom tetrahedral cells, using the lattice parameters produced by the VFF relaxation calibrated by experimental data and ELK+r2SCAN relaxation.

[0231] The lattice parameters in Table 2A in FIG. 2A,are in general very similar to the lattice parameter "a" in Table 1, of the above referenced work by J. Ziembicki et al. The lattice parameters in Table 2B are in general very similar to the lattice parameters "a" and "b" in Table 1, of the above referenced work by Peihong Zhang et al.

[0232] Table 3A in FIG. 3A, has the data for the ZB cells, and Table 3B in FIG. 3B, has the data for the 5-atom tetrahedral cells, strained to Si (001) surfaces, using the lattice parameters produced by the VFF relaxation calibrated by experimental data and ELK+r2SCAN relaxation with epitaxial pseudomorphic constraint. The band-gap data was calculated with Becke & Johnson (mBJ) or Tran-Blaha exchange and correlation potential, with the c-parameter being fixed at 1.04, and with Spin-Orbit Coupling.

[0233] LDA is also known for severely underestimating the magnitude of certain band-gaps, which in the case of Ge comes out being nearly zero eV, instead of the ~0.74eV at zero degrees Kelvin, and 0.67 eV at room temperature. The band-structures were calculated with the pseudo-potential plane-wave code, using the Modified Becke & Johnson (mBJ) or Tran-Blaha exchange and correlation potential, with the c-parameter being fixed at 1.04, and with Spin-Orbit Coupling, which produces extremely accurate results for bulk Si, bulk Ge, Ge strained to Si, and Si1-yCyalloys strained to Si, as first published by C. Augusto, L. Forester, " Novel Si-Ge-C superlattices and their applications"; Solid-State Electr., Vol. 110 (8), 1-9 (2015), DOI: 10.1016 / i.sse.2015.01.019.

[0234] However, it should be noted that in general, the best results with the Modified Becke & Johnson (mBJ) or Tran-Blaha (TB09) exchange and correlation potential, are obtained only with allelectron codes, and the results obtained with pseudo-potential codes are not as good.

[0235] It is important to note that, for 3D structurally relaxed CSi, CGe, and SnC, the band-gaps calculated by J. Ziembicki et al, are larger than the band-gaps calculated with cpw2000, but both calculations are in qualitative agreement for the k-point coordinates of the Valance Band Maximum (Gamma point for all these materials), and for the k-point coordinates of the Conduction Band Minimum, X, Y, Z, for CSi and CGe, and Gamma for CSn. For CSi, CGe, and SnC, strained to Si (00 1), the k-point coordinates for Conduction Band Minimum (CBM) are the Z point (boundary of the BZP AT E N T Docket No. QS3101 along the direction of epitaxial growth) for CSi and CGe and for CSn it remains at Gamma but the gap becomes zero. For CSi and CGe, the Valence Band Maximum (VBM) remains at Gamma, but for CSn the VBM becomes a saddle.

[0236] 9. Aperiodic / Quasiperiodic SLs

[0237] Typical superlattices, such as those described in U. S. Patent 9640616B2, " Superlattice materials and applications", consist of a superlattice cell being repeated multiple time so as to form a superlattice, each cell having multiple atomic planes, in which at least two of the atomic planes in the cell have different chemical compositions, thus forming periodic heterostructures.

[0238] However, it is also possible to form aperiodic or quasiperiodic heterostructures or superlattices. An example of such structures was experimentally demonstrated by R. Merlin, K. Bajema, R. Clarke, F-Y. Juang, and P. K. Bhattacharya. " Quasiperiodic GaAs-AIAs heterostructures", Physical Review Letters 55, no. 17 (1985), pp. 1768, DOI: 10.1103 / PhysRevLett.55.1768

[0239] In this experimental work, the superlattice consisted of "alternating layers of GaAs and AlAs to form a Fibonacci sequence in which the ratio of incommensurate periods is equal to the golden mean T". Other types of aperiodic or quasiperiodic sequences include the Cantor, Rudin-Shapiro, Thue-Morse, etc. In this disclosure, band structure plots are shown, of quasiperiodic superlattices formed by stacking Zinc-Blende blocks of group-IV materials, in sequences according to different methods.

[0240] FIG. 47A shows a crystal structure constructed on top of a Si (001) surface, of the cell for the aperiodic or quasiperiodic SL constructed following the Cantor series of order N=3, using ZB cells of SiGe and Zinc-ZB cells of PbC. FIG. 47B shows a band structure plot of a crystalline cell strained to a Si (001) surface.

[0241] The construction of the superlattice cell follows the approach used in the following reference: F. R. Gomez, N. Porras-Montenegro, O. N. Oliveira, Jr., and J. R. Mejia-Salazar, " Giant Second-Harmonic Generation in Cantor-like Metamaterial Photonic Superlattices", ACS Omega 20183 (12), pp. 17922-17927, DOI: 10.1021 / a cso m eg.8 b 02 37.

[0242] FIG. 48A shows a crystal structure constructed on top of a Si (001) surface, of the cell for the aperiodic or quasiperiodic SL constructed following the Fibonacci series of order N=3, using ZB cells of GeC and diamond cells of Si to form two identical GeCQWs having two Si QBs of different thicknesses. FIG. 48B shows a band structure plot of a crystalline cell strained to a Si (001) surface.

[0243] The construction of the superlattice cell follows the approach used in the following reference: J. Hendrickson, B. C. Richards, J. Sweet, G. Khitrova, A. N. Poddubny, E. L. Ivchenko, M. Wegener, andP AT E N T Docket No. QS3101 H. M. Gibbs, " Excitonic polaritons in Fibonacci quasicrystals", Opt. Express 16, 15382-15387 (2008), DOI: 10.1364 / QE.16.015382.

[0244] FIG. 49A shows a crystal structure constructed on top of a Si (001) surface, of the cell for the aperiodic or quasiperiodic SL constructed following the Rudin-Shapiro series of order N=3, using ZB cells of SiGe and ZB cells of PbC. FIG. 49B shows a band structure plot of a crystalline cell strained to a Si (001) surface.

[0245] The construction of the superlattice cell follows the approach used in the following reference: H. A. Gomez-Urrea, M. Toledo-Solano, M. E. Mora-Ramos, E. Reyes-Gomez, " Properties of plasmonpolariton modes in one-dimensional photonic superlattices made of Rudin-Shapiro bases", Opt. Quant. Electron. (2013) 45:813-828, DOI: 10.1007 / sll082-013-9683-3.

[0246] FIG. 50A shows a crystal structure constructed on top of a Si (001) surface, of the cell for the aperiodic or quasiperiodic SL constructed following the Thue-Morse series of order N=4, using ZB cells of SiGe and ZB cells of PbC. FIG. 50B shows a band structure plot of a crystalline cell strained to a Si (0 0 1) surface. The construction of the superlattice cell follows the approach used in the following reference: S. Savoia, G. Castaldi, and V. Galdi, " Optical nonlocality in multilayered hyperbolic metamaterials based on Thue-Morse superlattices", Physical Review B 87, 235116 (2013), DOI:10.1103 / PhysRevB.87.235116.

[0247] 10. Properties of Non-Centrosymmetric Crystals

[0248] By definition, the ZB and 5-atom tetrahedral cells are non-centrosymmetric crystals. Many QWs and SLs built with ZB cells and / or 5-atom tetrahedral cells are also non-centrosymmetric crystals. Consequently the properties inherent to non-centrosymmetric crystals, such as nonlinear optoelectronic properties, that are determined by point group and space group symmetries, may be significant in some of these materials.

[0249] A recent comprehensive review paper by M. Suarez-Rodriguez, F. de Juan, I. Souza, et al, " Nonlinear transport in non-centrosymmetric systems", Nat. Mater. 24, 1005-1018 (2025), DOI:provides tables listing point group symmetry and the types of nonlinear properties that the corresponding crystal may have. The following are the nonlinear properties:

[0250] NLC: Non-Linear Conductivity - nonlinear transport effect at zero (magnetic) field.

[0251] NLMC: nonlinear magnetoconductivity.

[0252] Longitudinal NLMC: unidirectional magnetoresistance and electrical magnetochiral anisotropy. Transversal NLMC: nonlinear planar Hall effect.P AT E N T Docket No. QS3101

[0253] According to Table SI in supplementary material of the above paper, several different materials discussed in this disclosure belong point group symmetries that inherently have non-trivial nonlineartransport properties, i.e., as having longitudinal and / or transversal components for NLC and NLMC. Naturally, the "magnitude" of the properties will depend on additional material-specific parameters.

[0254] Several different materials discussed in this disclosure belong to the following point groups (SG), listed in the first column of Table SI: Row 4 (crystal of FIG.31), Row 7 (crystal of FIGs.40A, 41A, 42A), Row 9 (crystal of FIG. 32), Row 14 (crystal of FIG. 39A).

[0255] Another recent publication covers the impact of crystal symmetry on the spin: B. Kilic, S. Alvarruiz, E. Barts, et al, " Universal symmetry-protected persistent spin textures in noncentrosymmetric crystals". Nat. Commun. 16, 7999 (2025), DOI: 10.1038 / s41467-025- 63136-4.

[0256] According to the results in this paper, several different materials discussed in this disclosure belong to the following space groups (SG), listed in the first column of Table SI (Supplementary note 4), in the supplementary material file: 25, 35, 44, 80, 81, 82, 92, 109, 111, 115, 119, 156, 160. All of these SGs are identified as having high-symmetry points, and / or lines, and / or planes, in the BZ with symmetry-protected persistent spin texture (SP-PST).

[0257] Consequently the materials belonging to some of these space groups could be used as injectors / detectors of spin polarized currents into / from silicon, for room temperature operation of spin devices, replacing the ferromagnetic materials used to demonstrate room temperature operation by S. Dash, S. Sharma, R. Patel, et al, " Electrical creation of spin polarization in silicon at room temperature", Nature 462, 491-494 (2009), DOI: 10.1038 / nature08570. The applications for these materials covers a wide range that includes, but is not limited to, magnetic memories, magnetic sensors, radio-frequency and microwave devices, logic and non-Boolean devices.

[0258] Key material-specific parameters are the quantum-geometric properties of Bloch electrons: Berry curvature, quantum metric, orbital magnetic moment and effective mass. First principles calculations with high precision are described in the following reference, J. L. Martins, C. L. Reis, I. Souza, " Precise quantum-geometric electronic properties from first principles", SciPost Phys. 19, 109 (2025), DOI: 10.21468 / SciPostPhys.19.4.109. These calculations can be performed with the abovereferenced open source cpw2000 DFT package.

[0259] Using the aforementioned DFT code cpw2000 to calculate these quantities for SnC and PbC, strained to Si (001), Si (110) and Si (111) substrates, the results reveal that both SnC and PbC have significantly larger Berry Curvature, Quantum Metric, and Orbital Magnetic Moment (or OrbitalP AT E N T Docket No. QS3101 Magnetization) than Tellurium, a reference material with notable topological properties. FIG. 52-Table 6 lists the results of these calculations for T = 0K.

[0260] The symmetry of crystals does not change between T = 0 K and T = 300 K, unless there is a phase change. It is well known that SiGe or SiGeC random alloys do not go through phases change when the temperature is varied in that range, and there is no reason to think that any of the other group-IV materials discussed in this disclosure suffer phase changes in this temperature range.[00261JA recent paper by S. Lannebere, T. G. Rappoport, T. A. Morgado, I. Souza, M. G. Silveirinha, " Symmetry Analysis of the Non-Hermitian Electro-Optic Effect in Crystals", DOI: arXiv:2502.03399v2, further explores the impact of crystal symmetry on optical properties of materials. In particular this work explores how "crystal symmetry tailors the non-Hermitian electro-optic effect arising from the Berry curvature dipole.", and how "how optical gain and attenuation can be controlled via symmetry and bias configurations".

[0262] Several superlattices and QW / QB structures discussed in this disclosure belong to the Category E of point group symmetry in Table II of the aforementioned paper by S. Lannebere. In page 5, it is stated that "... category E materials are optically active and piezoelectric".

[0263] In page 6 it is stated " Materials from category E also lead to pure linear dichroic gain. For the group 4 the BD tensor is such that Dxx= -Dyy= Do and Dxy= Dyx(see Table II)", and some materials discussed in this disclosure belong to group 4 (space group 80), such as CGezSnz strained to Si (001), whose band structure plot is shown in FIG. 35.

[0264] According to Table 2 in G. H. Fecher, J. Ku bier, C. Felser, " Chirality in the Solid State: Chiral Crystal Structures in Chiral and Achiral Space Groups", Materials. 2022; 15(17):5812. DOI:10.3390 / ma15175812, a few of the materials described in this disclosure have chiral structures, such as the space group 80, which in Table 1 (Laue Class 4), possesses the following properties: enantiomorphism (chirality), polar (pyroelectric, ferroelectric), optical active, piezoelectric, and nonlinear optics.

[0265] The reason for GeC strained to Si (1 1 0) to have significant quantum-geometric properties, while GeC strained to Si (001) and GeC strained to Si (111) not to have them, is related to the same factors that QWs of AIGaAs / GaAs epitaxially grown on (110) surface have such properties, but lacking them for the (0 0 1) and (1 1 1) surfaces, as discussed by H. Diehl, V. A. Shalygin, V. V. Bel'kov, Ch. Hoffmann, S. N. Danilov, T. Herrle, S. A. Tarasenko, D. Schuh, Ch. Gerl, W. Wegscheider, " Spin photocurrents in (HO)-grown quantum well structures", New J. Phys. 9, 349, 2007, DOI:■10.1088 / 1367-2630 / 9 / 9 / 349.P AT E N T Docket No. QS3101

[0266] In view of the foregoing, the ordered alloys, QWs, and SLs (periodic and aperiodic) strained to Si (001) surfaces, described in this disclosure, are promising building blocks for spintronic devices and spin qubits.

[0267] 11. Engineered In-Plane Anisotropies

[0268] For epitaxially grown materials it is trivial to engineer an anisotropy between the direction of epitaxial growth (perpendicular to the substrate) versus the two in-plane directions (parallel to the substrate), and typically, the overall material properties are identical for each of the two in-plane directions.

[0269] However, it is desirable to have the possibility of engineering anisotropies between the two in-plane directions, but that is not feasible with conventional approaches to engineer QWs / QBs and SLs. Herein it is disclosed how to achieve this goal, using group-IV materials to illustrate such possibility.

[0270] The simulation results for diamond or ZB cells strained to any of the main crystallographic surfaces of Si, show that all the band-gaps are smaller than Silicon's, some being zero, and others being significantly negative, i.e., being semi-metals (some trivial and some topological). Consequently silicon is the natural QB, and the other materials form the QWs.

[0271] It is important to note that in typical lll-V materials both QWs and QBs, can be ZB cells, for example GaAs QW and AlAs QB, resulting in a double heterojunction having symmetric interfaces between the QW and the QB, in the sense that an anion is always bonded only to cations and vice versa, even though the anions and the cations in the QW and QB belong to different rows of the periodic table.

[0272] Qn the other hand, having one or multiple group-IV ZB cells as the QW and Silicon (multiple diamond cells) as the QB, necessarily results in a double heterojunction having asymmetric interfaces between the QW and the QB, which in turn may result in interface states and internal electric fields, due to charge dislocation inside the ZB QW region.

[0273] Several ZB cell QWs, sandwiched between silicon QBs, are shown in FIGs. 39 through 43, in which FIGs. 39, 40, 41, 42, show QWs made of a single ZB cell of CSi, CGe, CSn, and CPb, respectively, each sandwiched between 15 diamond cells of Si. In all these cases, there is an asymmetry at the interfaces of the double heterojunction, except for CSi.

[0274] This interface asymmetry produces an anisotropy in the oscillator strength along the X-direction versus the Y-direction, both in the plane parallel to the substrate. These directions are theP AT E N T Docket No. QS3101 directions of oscillation of the electric field of the photon, and therefore refer to photons traveling perpendicularly to the substrate.

[0275] Symmetric double heterojunction interfaces and isotropic oscillator strengths can be obtained by making C the center of the QW, to be bonded to the same chemical species (Si, Ge, Sn, Pb) on both sides, i.e., below and above the atomic plane populated with C. This results in having the same chemical species interfacing with the silicon QB, thereby eliminating internal electric fields, and the bonds formed by C with the atomic plane above it are rotated by 90 degrees with respect to the bonds with the atomic plane below it. Conversely, symmetric interfaces can also be made by placing Si, or Ge, or Sn, or Pb, at the center of the QW and placing C on both sides, i.e., below and above the atomic plane populated with Si, or Ge, or Sn, or Pb.

[0276] For example, instead of having (CGe)-(Si)n, one could have (GeGeCGeGe)-(Si)n, where "n" is the number of atomic planes for the Si QB, as shown in FIG. 44A left, for (001) surface, whose band structure is shown in FIG. 44B. Similarly, one can have isotropic oscillator strength for (SnCSn)-(Si)n, FIG. 45A left, for (001) surface, whose band structure is shown in FIG. 45B, instead of (CSn)-(Si)n.

[0277] It is desirable to have the largest oscillator strength possible, for maximum optoelectronic efficiency, and have the ability to emit or absorb photons with electric field oscillating along any direction parallel to the substrate. This can be done by engineering in-plane anisotropies, which preferably are implemented by having separate, but identical, QW / QB layers tuned to each of the inplane directions of interest.

[0278] A first method to accomplish this is by stacking those separate, but identical QW / QB on top of each other, with suitably large QB thickness separating them, and having an odd number of atomic planes of the QB between them. This requires atomic-layer control of the total thickness of the QB between the QWs. A structure that implements this method is shown in FIG. 53, which now has the same oscillator strengths along the X-direction and the Y-direction.

[0279] A second method to achieve this is by having the separate, but identical, QW / QB layers side by side. There are several variations to implement the second method. In FIG. 54A and 54B, one has the same number of atomic planes for each chemical species in the cell, but one has a large oscillator strength along the X-direction while the other along the Y-direction.

[0280] A first variation is to execute two separate epitaxial growths on the same mono-terrace surface, in which one of the growths inserts an extra atomic plane of silicon before growing the QW layers.P AT E N T Docket No. QS3101

[0281] A second variation is to execute a single epitaxial growth on two different terraces of the substrate surface, in which the step height between those two terraces is an odd integer multiple of a single atomic plane.

[0282] The cases illustrated in FIGs. 54A, 54B, show the oscillator strength for the in-plane directions varies continuously from the maximum value along such direction to a minimum value to the direction at a 90 degree angle.

[0283] The method of FIG. 53 is suitable to fabricate a single device, while the method of FIGs. 54A, 54B, can also be used to fabricate a single optoelectronic device, for example through coupling of both sets of QWs / QBs to a single optical cavity, while being electrically controlled separately, thereby enabling more complex combinations of light emission with different weights for one or the other polarization direction.

[0284] It should be noted that in conventional epitaxial growth of semiconductor layers, of group-IV, or lll-V, or ll-VI, etc., the epitaxial growth takes place across steps and in multiple terraces, without any control, which makes it impossible to explore any of the crystal engineering just described in the previous paragraphs. Only the methods described above allow, with particular care about atomic steps and terraces, allow the ultimate crystal engineering in a controllable and deterministic manner.

[0285] In superlattices, anisotropy can appear when C is bonded to two different chemical species, for example Si-C-Ge (or Ge-C-Si) bonds, and that the oscillator strengths can be made isotropic by precluding such mixed bonds, and enforcing only Ge-C-Ge (or Si-C-Si) types of bonds.[00286112. New Devices Enabled by New Materials

[0287] The epitaxially grown ZB cells, and / or 5-atom tetrahedral cells, and their stacking into superlattices, can be incorporated into CMOS wafers, including Silicon-Photonics wafers and CMOS Image Sensor (CIS) wafers, either on the front-side and / or on the back-side of said CMOS wafers, as described by Carlos Jorge Augusto, PCT / US2024 / 050151, W02025076496, " Optoelectronic, Thermoelectronic, Photonic, Materials and Devices, Fabricated on The Back Side Surface of CMOS Wafers".

[0288] Said epitaxially grown layers / materials possess a variety of electronic band structures which make them desirable to be part of optoelectronic devices, to provide a variety of functionalities, such as light absorption, light emission, light waveguiding, light modulation, light amplification, conversion of photon frequency / energy (i.e., upconvert or down convert photon frequency), provide photocharge multiplication (i.e., gain). Said epitaxially grown layers / materials also possess a variety ofP AT E N T Docket No. QS3101 phononic band structures which make them desirable to be part of thermoelectric devices, to provide cooling or heating, or to convert heat or temperature gradients into electricity, for energy harvesting.

[0289] The aforementioned materials, metamaterials, and devices incorporating them, may be used to interact with light across a very wide range of the electromagnetic spectrum, from Gamma rays, X-rays, UV, Visible, NIR, SWIR, MWIR, LWIR, VLWIR, FIR, and also TeraHertz. This wide spectral range is possible because metamaterials comprising group-IV elements, from the lightest (Carbon) to the heaviest (Lead), enable different types of physics regarding light-matter interactions for photoabsorption, photo-emission, and different types of light manipulation.

[0290] The variety of band structures, band-gaps, and consequently of heterojunction band alignments or offsets, afforded by the different ZB cells, 5-atom tetrahedral cells, and the stacking of multiple such cells into superlattices, provide new degrees of freedom to engineer a wide variety of heterojunction devices.

[0291] The results of DFT calculations for band structures indicate that GeC strained to Si (001), has a band-gap of 0.02 eV (FIG. 12B), and the results for a QW consisting of one ZB cell of GeC positioned in the middle of 30 ZB cells of Silicon QB, show (FIG. 45B) very quantized energy levels for electrons, but minibands for holes. These results indicate the existence of deep potential well for electrons but no potential well for holes, with the minibands being formed by bound states in the continuum (BICs).

[0292] In view of the small but positive band-gap for GeC, the lack of a potential well for holes indicates that the potential well for electrons is as large as the band-gap of the QB made of Silicon, or even larger. Since GeC might form a broken-gap with Si, or be very close to that type of band alignment, it definitely forms a broken-gap in heterojunctions with pure Ge, and with Sio.sGeo.s ordered alloy (formed by stacking ZB cells of SiGe).

[0293] DFT simulation results show (FIG.8B) that pure Ge strained to Si (001) has a band-gap of 0.50 eV and has a type-ll band alignment with its conduction band above the conduction band of Silicon. While the type-ll alignment is generally accepted the values for the band offset are somewhere between 0.05 eV and 0.15 eV. Given the information above about Ge and GeC strained to Si (001), a linear interpolation of band-gap and band offsets for Gei-zCz(z < 0.5) ordered and disordered (random) alloys strained to Si (001), leads to band-gaps ranging between 0.02 eV and 0.50 eV. The conduction band offsets are in the range of ~+0.05 eV for pure Ge and ~-1.1 eV for GeC, and the valence band offsets are in the range of ~+0.84 eV for Ge and ~0.0 eV for GeC.

[0294] Therefore, epitaxial Gei.zCz(z < 0.5) films strained to Si (0 0 1), with a gradient in Carbon concentration can form a gradient in the conduction band edge, which can be useful as the Base layer of aggressively scaled (layer thickness wise) p-n-p HBTs (in which Emitter and Collector can be pureP AT E N T Docket No. QS3101 silicon). This, along with standard Sii.xGex(or Sii-x.yGexCy) alloys as the Base of n-p-n HBTs, can be used to fabricate fully differential HBT circuits. It should be noted that the novel methods to form SiGe ordered alloys discussed in this disclosure may provide advantages, over standard random Sii-xGex(or Sii-x.yGexCy) alloys, as the Base layers of n-p-n HBTs.

[0295] Epitaxial Gei.zCz(z < 0.5) films strained to Si (00 1), heavily doped with n-type dopants, can also be useful as the source layer for p-type Tunnel-MOSFETs, thus realizing the complementary device to the n-type Tunnel-MOSFET, having a heavily doped with p-type dopants Sii.xGex(or Sii-x.yGexCy) source region.

[0296] Examples of other devices benefitting of new group-IV alloy compositions enabled by the inventions described in this disclosure include, Auger gain regions in HBTs and Tunnel-FETs, n-type quantum cascade lasers, as well as a variety of devices requiring conduction band offsets sufficiently large for quantum confinement of electrons at room temperature. Any of said devices may incorporate charge multiplication regions, resonant tunneling regions, or be part of resonant nonvolatile memory structures, or part of superlattice Bloch oscillators, part of photodiodes, edge emitting laser, vertical emitting lasers, HBT-lasers, etc.

[0297] As discussed earlier, materials with symmetries belonging to space groups 1 and 80 (Laue Classes 1 and 4), inherently possess the following properties: enantiomorphism (chirality), polar (pyroelectric, ferroelectric), optical active, piezoelectric, and nonlinear optics. The ability to fabricate materials with such properties in a deterministic way, and monolithically integrated with CMOS (and BiCMOS), will enable devices with completely new functionalities, and unprecedented size, weight, power consumption and cost (SWaP-C).

[0298] Among the properties of non-centrosymmetric crystals, the nonlinear Hall effect can be used for new types of devices, which include rectifiers without the need to fabricate pn-junctions. Without pn-junctions and with ohmic contacts having the same Schottky barrier height, there are no built-in electric fields. Consequently there are no dark currents, even at room temperature, and such materials can be used to perform sensing of photons with energies much smaller than the band-gaps of the materials. They can also perform energy harvesting from a wide range of electromagnetic wavelengths, from RF to Microwaves, to Terahertz. Conceptually it could be possible to extend sensing and harvesting to shorter wavelengths into the Far Infra-Red (FIR) and Long Wavelength Infra-Red (LWIR), and perhaps the Mid-Wavelength Infra-Red (MWIR).

[0299] Materials discussed in this disclosure that belong to the symmetry groups that should exhibit piezoelectricity, can be used to emit or sense ultrasound waves, and can be used to dynamically apply strain to the material itself, or to apply strain laterally or vertically (i.e., stacked) to adjacent layers. InP AT E N T Docket No. QS3101 the latter case it can be used to change the resonant wavelength in cavities of VCSELs. It can also be used for pressure measurement. The nano-structuring, in 1D or 2D, or 3D, of any of the materials described in this disclosure further increases the ability to obtain novel or enhanced physical properties

[0300] FIG. 55 is a flowchart illustrating a process 5500 for fabricating a semiconductor device, according to some embodiments of the disclosed technologies. The process 5500 may be employed to fabricate the devices disclosed herein. The elements of process 5500 are presented in one arrangement. However, it should be understood that one or more elements of the process may be performed in a different order, in parallel, omitted entirely, and the like. Furthermore, the process 5500 may include other elements in addition to those presented.

[0301] Referring to FIG. 55, the process 5500 may include providing a Si substrate having a monoterrace surface or multiple terrace surfaces, at 5502.

[0302] The process 5500 may include epitaxially growing multiple Group-IV elements by chemical vapor deposition (CVD), wherein the multiple Group-IV elements are pseudomorphically strained to the Si substrate, at 5504.

[0303] The process 5500 may include deterministically predefining a chemical and isotopic composition of the multiple Group-IV elements, as well as atomic configuration in each atomic plane, through selection of CVD chemical precursors having a desired composition and atomic configuration to be adsorbed at a surface of the Si substrate and incorporated into a solid growth front of the multiple Group-IV elements, at 5506.

[0304] In some embodiments, the multiple Group-IV elements are arranged in ordered alloys.

[0305] In some embodiments, the multiple Group-IV elements are arranged in quantum wells and quantum barriers. In some embodiments, the quantum wells and quantum barriers form double heterojunctions, and are epitaxially grown on mono-terrace surfaces. In such embodiments, the thickness of the quantum wells is an even integer number of atomic planes; and the thickness of the quantum barriers, between adjacent quantum wells, is an odd integer number of atomic planes.

[0306] In some embodiments, the quantum wells and quantum barriers form double heterojunctions, and are epitaxially grown on mono-terrace surfaces. In such embodiments, the thickness of the quantum wells is an even integer number of atomic planes; and the thickness of the quantum barriers, between adjacent quantum wells, is an even integer number of atomic planes.

[0307] In some embodiments, the quantum wells and quantum barriers form double heterojunctions, and are epitaxially grown on two mono-terrace surfaces, separated by a step having a height that is an odd integer multiple of a single atomic plane. In such embodiments, the thicknessP AT E N T Docket No. QS3101 of the quantum wells is an even integer number of atomic planes; and the thickness of the quantum barriers, between adjacent quantum wells, is an odd integer number of atomic planes.

[0308] In some embodiments, the quantum wells and quantum barriers form double heterojunctions, and are epitaxially grown on two mono-terrace surfaces, separated by a step having a height that is an odd integer multiple of a single atomic plane. In such embodiments, the thickness of the quantum wells is an even integer number of atomic planes; and the thickness of the quantum barriers, between adjacent quantum wells, is an even integer number of atomic planes.

[0309] In some embodiments, the multiple Group-IV elements are arranged in periodic superlattices.

[0310] In some embodiments, the multiple Group-IV elements are arranged in aperiodic or quasiperiodic superlattices.

[0311] In some embodiments, the multiple Group-IV elements include a first Group-IV element and a second Group-IV element, where the the first Group-IV element and the second Group-IV element are not the same element. The first Group-IV element and the second Group-IV element may be selected from the set of C, Si, Ge, Sn, and Pb. The multiple Group-IV elements may form an ordered alloy, where each atom of the first Group-IV element is bonded to four atoms of the second Group-IV element, and where each atom of the second Group-IV element is bonded to four atoms of the first Group-IV element, in a configuration formed by stacking Zinc-Blende cells of the ordered alloy.

[0312] In some embodiments, the multiple Group-IV elements include a first Group-IV element and a second Group-IV element, where the first Group-IV element and the second Group-IV element are not the same element. The first Group-IV element and the second Group-IV element may be selected from the set of C, Si, Ge, Sn, and Pb. The multiple Group-IV elements may an ordered alloy, in which each atom of the first Group-IV element is bonded to four atoms of the second Group-IV element, in a configuration formed by stacking 5-atom tetrahedral cells of the ordered alloy.

[0313] In some embodiments, the multiple Group-IV elements include a first Group-IV element, a second Group-IV element, and a third Group-IV element, where none of the first Group-IV element, the second Group-IV element, and the third Group-IV element are the same element. The first Group-IV element, the second Group-IV element, and the third Group-IV element may be selected from the set of C, Si, Ge, Sn, and Pb. The multiple Group-IV elements may form an ordered alloy, in which each atom of the first Group-IV element is bonded to one atom of the second Group-IV element and to three atoms of the third Group-IV element, in a configuration formed by stacking 5-atom tetrahedral cells of the ordered alloy.

[0314] In some embodiments, the multiple Group-IV elements include a first Group-IV element, a second Group-IV element, a third Group-IV element, and a fourth Group-IV element, where none ofP AT E N T Docket No. QS3101 the first Group-IV element, the second Group-IV element, the third Group-IV element, and the fourth Group-IV element, are the same element. The first Group-IV element, the second Group-IV element, the third Group-IV element, and the fourth Group-IV element, may be selected from the set of C, Si, Ge, Sn, and Pb. The multiple Group-IV elements form an ordered alloy, in which each atom of the first Group-IV element is bonded to one atom of the second Group-IV element, to one atom of the third Group-IV element, and to two atoms of the fourth Group-IV element, in a configuration formed by stacking 5-atom tetrahedral cells of the ordered alloy.

[0315] In some embodiments, the multiple Group-IV elements include a first Group-IV element, a second Group-IV element, a third Group-IV element, a fourth Group-IV element, and a fifth Group-IV element, where none of the first Group-IV element, the second Group-IV element, the third Group-IV element, the fourth Group-IV element, and the fifth Group-IV element, are the same element. The first Group-IV element, the second Group-IV element, the third Group-IV element, the fourth Group-IV element, and the fifth Group-IV element, may be selected from the set of C, Si, Ge, Sn, and Pb. The multiple Group-IV elements may form an ordered alloy, in which each atom of the first Group-IV element is bonded to one atom of the second Group-IV element, to one atom of the third Group-IV element, and to one atom of the fourth Group-IV element, and to one atom of the fifth Group-IV element, in a configuration formed by stacking 5-atom tetrahedral cells of the ordered alloy.

[0316] In some embodiments, the multiple Group-IV elements include a first Group-IV element and a second Group-IV element, where the first Group-IV element and the second Group-IV element are not the same element. The first Group-IV element and the second Group-IV element may be selected from the set of C, Si, Ge, Sn, and Pb. The multiple Group-IV elements may form an ordered alloy, in which each atom of the first Group-IV element has one bond to another atom of the first Group-IV element, and has three bonds to atoms of the second Group-IV elements.

[0317] Referring again to FIG. 55, the process 5500 may include admixing or co-flowing the CVD precursors with elemental precursors, to epitaxially grow Group-IV random alloys with wide range of C, Si, Ge, Sn, Pb, compositions, between the composition of the precursors and the composition of the elemental precursor, at 5508.

[0318] The process 5500 may include pulsing the CVD precursors alternatively with elemental precursors, to epitaxially grow Group-IV random alloys and aperiodic or quasiperiodic superlattices, at 5510.

Claims

P AT E N T Docket No. QS3101 ClaimsWhat is claimed is:

1. A semiconductor device comprising:a Si substrate having a mono-terrace surface or multiple terrace surfaces; and multiple Group-IV elements epitaxially grown by chemical vapor deposition (CVD) and pseudomorphically strained to the Si substrate;wherein a chemical and isotopic composition of the multiple Group-IV elements, as well as atomic configuration in each atomic plane, are deterministically predefined through selection of CVD chemical precursors having a desired composition and atomic configuration to be adsorbed at a surface of the Si substrate and incorporated into a solid growth front of the multiple Group-IV elements.

2. The semiconductor device of claim 1, wherein:the multiple Group-IV elements comprise a first Group-IV element and a second Group-IV element;the first Group-IV element and the second Group-IV element are not the same element; the first Group-IV element and the second Group-IV element are selected from the set of C, Si, Ge, Sn, and Pb; andthe multiple Group-IV elements form an ordered alloy, wherein each atom of the first Group-IV element is bonded to four atoms of the second Group-IV element, and wherein each atom of the second Group-IV element is bonded to four atoms of the first Group-IV element, in a configuration formed by stacking Zinc-Blende cells of the ordered alloy.

3. The semiconductor device of claim 1, wherein:the multiple Group-IV elements comprise a first Group-IV element and a second Group-IV element;the first Group-IV element and the second Group-IV element are not the same element; the first Group-IV element and the second Group-IV element are selected from the set of C, Si, Ge, Sn, and Pb; andthe multiple Group-IV elements form an ordered alloy, in which each atom of the first Group-IV element is bonded to four atoms of the second Group-IV element, in a configuration formed by stacking 5-atom tetrahedral cells of the ordered alloy.P AT E N T Docket No. QS3101 4. The semiconductor device of claim 1, wherein:the multiple Group-IV elements comprise a first Group-IV element, a second Group-IV element, and a third Group-IV element;none of the first Group-IV element, the second Group-IV element, and the third Group-IV element are the same element; andthe first Group-IV element, the second Group-IV element, and the third Group-IV element are selected from the set of C, Si, Ge, Sn, and Pb;the multiple Group-IV elements form an ordered alloy, in which each atom of the first Group-IV element is bonded to one atom of the second Group-IV element and to three atoms of the third Group-IV element, in a configuration formed by stacking 5-atom tetrahedral cells of the ordered alloy.

5. The semiconductor device of claim 1, wherein:the multiple Group-IV elements comprise a first Group-IV element, a second Group-IV element, a third Group-IV element, and a fourth Group-IV element;none of the first Group-IV element, the second Group-IV element, the third Group-IV element, and the fourth Group-IV element, are the same element;the first Group-IV element, the second Group-IV element, the third Group-IV element, and the fourth Group-IV element, are selected from the set of C, Si, Ge, Sn, and Pb; andthe multiple Group-IV elements form an ordered alloy, in which each atom of the first Group-IV element is bonded to one atom of the second Group-IV element, to one atom of the third Group-IV element, and to two atoms of the fourth Group-IV element, in a configuration formed by stacking 5-atom tetrahedral cells of the ordered alloy.

6. The semiconductor device of claim 1, wherein:the multiple Group-IV elements comprise a first Group-IV element, a second Group-IV element, a third Group-IV element, a fourth Group-IV element, and a fifth Group-IV element;none of the first Group-IV element, the second Group-IV element, the third Group-IV element, the fourth Group-IV element, and the fifth Group-IV element, are the same element; the first Group-IV element, the second Group-IV element, the third Group-IV element, the fourth Group-IV element, and the fifth Group-IV element, are selected from the set of C, Si, Ge, Sn, and Pb; andthe multiple Group-IV elements form an ordered alloy, in which each atom of the first Group-IV element is bonded to one atom of the second Group-IV element, to one atom of the thirdP AT E N T Docket No. QS3101 Group-IV element, and to one atom of the fourth Group-IV element, and to one atom of the fifth Group-IV element, in a configuration formed by stacking 5-atom tetrahedral cells of the ordered alloy.

7. The semiconductor device of claim 1, wherein:the multiple Group-IV elements comprise a first Group-IV element and a second Group-IV element;the first Group-IV element and the second Group-IV element are not the same element; the first Group-IV element and the second Group-IV element are selected from the set of C, Si, Ge, Sn, and Pb; andthe multiple Group-IV elements form an ordered alloy, in which each atom of the first Group-IV element has one bond to another atom of the first Group-IV element, and has three bonds to atoms of the second Group-IV elements.

8. The semiconductor device of claim 1, wherein:the multiple Group-IV elements are arranged in ordered alloys.

9. The semiconductor device of claim 1, wherein:the multiple Group-IV elements are arranged in quantum wells and quantum barriers.

10. The semiconductor device of claim 1, wherein:the multiple Group-IV elements are arranged in periodic superlattices.

11. The semiconductor device of claim 1, wherein:the multiple Group-IV elements are arranged in aperiodic or quasiperiodic superlattices.

12. The semiconductor device of claim 1, wherein:the CVD precursors are admixed, or co-flowed, with elemental precursors, to epitaxially grow Group-IV random alloys with wide range of C, Si, Ge, Sn, Pb, compositions, between the composition of the precursors of claim 1 and the composition of the elemental precursor.

13. The semiconductor device of claim 1, wherein:the CVD precursors are pulsed alternatively with elemental precursors, to epitaxially grow Group-IV random alloys and aperiodic or quasiperiodic superlattices.P AT E N T Docket No. QS310114. The semiconductor device of claim 9, wherein:the quantum wells and quantum barriers forming double heterojunctions, are epitaxially grown on mono-terrace surfaces;the thickness of the quantum wells is an even integer number of atomic planes; and and the thickness of the quantum barriers, between adjacent quantum wells, is an odd integer number of atomic planes.

15. The semiconductor device of claim 9, wherein:the quantum wells and quantum barriers form double heterojunctions, are epitaxially grown on mono-terrace surfaces;the thickness of the quantum wells is an even integer number of atomic planes; and the thickness of the quantum barriers, between adjacent quantum wells, is an even integer number of atomic planes.

16. The semiconductor device of claim 9, wherein:the quantum wells and quantum barriers form double heterojunctions, and are epitaxially grown on two mono-terrace surfaces, separated by a step having a height that is an odd integer multiple of a single atomic plane;the thickness of the quantum wells is an even integer number of atomic planes; and the thickness of the quantum barriers, between adjacent quantum wells, is an odd integer number of atomic planes.

17. The semiconductor device of claim 9, wherein:the quantum wells and quantum barriers form double heterojunctions, and are epitaxially grown on two mono-terrace surfaces, separated by a step having a height that is an odd integer multiple of a single atomic plane;the thickness of the quantum wells is an even integer number of atomic planes; and the thickness of the quantum barriers, between adjacent quantum wells, is an even integer number of atomic planes.

18. The semiconductor device of claim 1, wherein:the multiple Group-IV elements are nano-structured in 1D, or 2D, or 3D.P AT E N T Docket No. QS3101 19. A method comprising:providing a Si substrate having a mono-terrace surface or multiple terrace surfaces; epitaxially growing multiple Group-IV elements by chemical vapor deposition (CVD), wherein the multiple Group-IV elements are pseudomorphically strained to the Si substrate; and deterministically predefining a chemical and isotopic composition of the multiple Group-IV elements, as well as atomic configuration in each atomic plane, through selection of CVD chemical precursors having a desired composition and atomic configuration to be adsorbed at a surface of the Si substrate and incorporated into a solid growth front of the multiple Group-IV elements.

20. The method of claim 19, wherein:the multiple Group-IV elements comprise a first Group-IV element and a second Group-IV element;the first Group-IV element and the second Group-IV element are not the same element; the first Group-IV element and the second Group-IV element are selected from the set of C, Si, Ge, Sn, and Pb; andthe multiple Group-IV elements form an ordered alloy, wherein each atom of the first Group-IV element is bonded to four atoms of the second Group-IV element, and wherein each atom of the second Group-IV element is bonded to four atoms of the first Group-IV element, in a configuration formed by stacking Zinc-Blende cells of the ordered alloy.

21. The method of claim 19, wherein:the multiple Group-IV elements comprise a first Group-IV element and a second Group-IV element;the first Group-IV element and the second Group-IV element are not the same element; the first Group-IV element and the second Group-IV element are selected from the set of C, Si, Ge, Sn, and Pb; andthe multiple Group-IV elements form an ordered alloy, in which each atom of the first Group-IV element is bonded to four atoms of the second Group-IV element, in a configuration formed by stacking 5-atom tetrahedral cells of the ordered alloy.

22. The method of claim 19, wherein:the multiple Group-IV elements comprise a first Group-IV element, a second Group-IV element, and a third Group-IV element;P AT E N T Docket No. QS3101 none of the first Group-IV element, the second Group-IV element, and the third Group-IV element are the same element;the first Group-IV element, the second Group-IV element, and the third Group-IV element are selected from the set of C, Si, Ge, Sn, and Pb; andthe multiple Group-IV elements form an ordered alloy, in which each atom of the first Group-IV element is bonded to one atom of the second Group-IV element and to three atoms of the third Group-IV element, in a configuration formed by stacking 5-atom tetrahedral cells of the ordered alloy.

23. The method of claim 19, wherein:the multiple Group-IV elements comprise a first Group-IV element, a second Group-IV element, a third Group-IV element, and a fourth Group-IV element;none of the first Group-IV element, the second Group-IV element, the third Group-IV element, and the fourth Group-IV element, are the same element;the first Group-IV element, the second Group-IV element, the third Group-IV element, and the fourth Group-IV element, are selected from the set of C, Si, Ge, Sn, and Pb; andthe multiple Group-IV elements form an ordered alloy, in which each atom of the first Group-IV element is bonded to one atom of the second Group-IV element, to one atom of the third Group-IV element, and to two atoms of the fourth Group-IV element, in a configuration formed by stacking 5-atom tetrahedral cells of the ordered alloy.

24. The method of claim 19, wherein:the multiple Group-IV elements comprise a first Group-IV element, a second Group-IV element, a third Group-IV element, a fourth Group-IV element, and a fifth Group-IV element;none of the first Group-IV element, the second Group-IV element, the third Group-IV element, the fourth Group-IV element, and the fifth Group-IV element, are the same element; the first Group-IV element, the second Group-IV element, the third Group-IV element, the fourth Group-IV element, and the fifth Group-IV element, are selected from the set of C, Si, Ge, Sn, and Pb; andthe multiple Group-IV elements form an ordered alloy, in which each atom of the first Group-IV element is bonded to one atom of the second Group-IV element, to one atom of the third Group-IV element, and to one atom of the fourth Group-IV element, and to one atom of the fifth Group-IV element, in a configuration formed by stacking 5-atom tetrahedral cells of the ordered alloy.P AT E N T Docket No. QS310125. The method of claim 19, wherein:the multiple Group-IV elements comprise a first Group-IV element and a second Group-IV element;the first Group-IV element and the second Group-IV element are not the same element; the first Group-IV element and the second Group-IV element are selected from the set of C, Si, Ge, Sn, and Pb; andthe multiple Group-IV elements form an ordered alloy, in which each atom of the first Group-IV element has one bond to another atom of the first Group-IV element, and has three bonds to atoms of the second Group-IV elements.

26. The method of claim 19, wherein:the multiple Group-IV elements are arranged in ordered alloys.

27. The method of claim 19, wherein:the multiple Group-IV elements are arranged in quantum wells and quantum barriers.

28. The method of claim 19, wherein:the multiple Group-IV elements are arranged in periodic superlattices.

29. The method of claim 19, wherein:the multiple Group-IV elements are arranged in aperiodic or quasiperiodic superlattices.

30. The method of claim 19, wherein:admixing or co-flowing the CVD precursors with elemental precursors, to epitaxially grow Group-IV random alloys with wide range of C, Si, Ge, Sn, Pb, compositions, between the composition of the precursors of claim 1 and the composition of the elemental precursor.

31. The method of claim 19, wherein:pulsing the CVD precursors alternatively with elemental precursors, to epitaxially grow Group-IV random alloys and aperiodic or quasiperiodic superlattices.

32. The method of claim 27, wherein:P AT E N T Docket No. QS3101 the quantum wells and quantum barriers form double heterojunctions, and are epitaxially grown on mono-terrace surfaces;the thickness of the quantum wells is an even integer number of atomic planes; and the thickness of the quantum barriers, between adjacent quantum wells, is an odd integer number of atomic planes.

33. The method of claim 27, wherein:the quantum wells and quantum barriers form double heterojunctions, and are epitaxially grown on mono-terrace surfaces;the thickness of the quantum wells is an even integer number of atomic planes; and the thickness of the quantum barriers, between adjacent quantum wells, is an even integer number of atomic planes.

34. The method of claim 27, wherein:the quantum wells and quantum barriers form double heterojunctions, and are epitaxially grown on two mono-terrace surfaces, separated by a step having a height that is an odd integer multiple of a single atomic plane;the thickness of the quantum wells is an even integer number of atomic planes; and the thickness of the quantum barriers, between adjacent quantum wells, is an odd integer number of atomic planes.

35. The method of claim 27, wherein:the quantum wells and quantum barriers form double heterojunctions, and are epitaxially grown on two mono-terrace surfaces, separated by a step having a height that is an odd integer multiple of a single atomic plane;the thickness of the quantum wells is an even integer number of atomic planes; and the thickness of the quantum barriers, between adjacent quantum wells, is an even integer number of atomic planes.

36. The method of claim 19, wherein:the multiple Group-IV elements are nano-structured in 1D, or 2D, or 3D.

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