Novel inorganic silyl and polysilyl derivatives of group v elements and methods of synthesis and use thereof for deposition

Abstract

This paper discloses precursors containing group V elements, their synthesis methods, and methods for using them in film deposition. These precursors are (SiR3). 3‑m A(Si a H 2a+1 ) m (SiR3) 3‑n‑p A(Si a H 2a+1 ) n (Si b H 2b+1 ) p or A(Si) a H 2a+1 (Si) b H 2b+1 (Si) c H 2c+1 Where a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c; m = 1 to 3; n = 1 to 2, p = 1 to 2, n + p = 2 to 3; A = As, P, Sb, Bi; and R is selected from C1 to C 10 Linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups. These synthetic methods include one-step, two-step, or three-step reactions between one or more halo(poly)silanes and a tri(trialkylsilyl) derivative of A, or one-pot mixed reactions between a mixture of two or three halo(poly)silanes and a tri(trialkylsilyl) derivative of A. Deposition methods include CVD, PECVD, ALD, PEALD, flowable CVD, HW-CVD, epitaxy, etc.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 293,328, filed December 23, 2021, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to precursors containing group V elements, methods for synthesizing them, and methods for using them in semiconductor film deposition. In particular, it relates to precursors containing group V elements having the following general formula:

[0004] (SiR3) 3-m A(Si a H 2a+1 ) m ,or

[0005] (SiR3) 3-n-p A(Si a H 2a+1 ) n (Si b H 2b+1 ) p or

[0006] A(Si a H 2a+1 (Si) b H 2b+1 (Si) c H 2c+1 )

[0007] in

[0008] a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c;

[0009] m = 1 to 3;

[0010] n = 1 to 2, p = 1 to 2, n + p = 2 to 3;

[0011] A = As, P, Sb, Bi; and

[0012] R is selected from C1 to C. 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups; relating to synthetic methods including one-step, two-step, or three-step reactions between one or more halo(poly)silanes and tris(trialkylsilyl) derivatives of A, or one-pot mixed reactions of mixtures of two or three halo(poly)silanes and tris(trialkylsilyl) derivatives of A; and relating to methods for depositing films containing Si and Group V elements, including CVD, PECVD, ALD, PEALD, flowable CVD, HW-CVD, epitaxy, etc. Background Technology

[0013] Thin films containing group V elements are used in a variety of applications, including p-doped Si or SiGe semiconductor channels and contact layers in solid-state transistors, non-volatile phase-change memories (PCMs), solar cells, III-V compounds, and optical storage materials. III-V compound semiconductors can be used in many different application areas, including transistors, optoelectronic devices such as bipolar transistors, field-effect transistors, lasers, infrared detectors, LEDs, wide-bandgap semiconductors, quantum well or quantum dot structures, solar cells, and monolithic microwave integrated circuits.

[0014] Several group III-V semiconductors exhibit features that make them attractive for use in solid-state electronic devices (e.g., high thermal stability, high electron mobility, and low band gap). However, group III-V semiconductors are more difficult to synthesize than the widely used group IV semiconductors, and the lack of suitable synthetic routes for group III-V compounds hinders their acceptance as alternatives to group IV compounds.

[0015] Some compounds (or V compounds) containing group V elements have been prepared using silyl and polysilyl ligands, namely P(SiH3)3, P(Si2H5)3, and As(SiH3). The use of these compounds in thin film deposition processes has been disclosed, specifically P(SiH3)3 as a phosphorus dopant for epitaxial applications (reference), producing highly stable crystal structures with average diamond-like symmetry by forming interconnected III-V-(IV)3 "structural units".

[0016] The relevant existing technologies include the following.

[0017] Tice et al. (Dalton Trans., 2010, 39(19), 4551-4558) disclosed the synthesis of P(SiH3)3 by P(SnMe3)3 + 3 SiH3Br → (SiH3)3P + 3 Me3SnBr.

[0018] Amberger et al. (Angew. Chem. Int. Ed. [Germany's Angewandte Chemie], 1962, 1, 52) disclosed the synthesis of (SiH3)3P in about 55% yield via 3 KPH2 + 3 SiH3Br → P(SiH3)3 + 2 PH3 + 3 KBr.

[0019] Amberger et al. (Angew. Chem. [Germany Angewandte Chemie], 1962, 74, 293) disclosed the synthesis and isolation of (SiH3)3As from the reaction between 3 KAsH2 + 3 SiH3Br → As(SiH3)3 + 2 AsH3 + 3 KBr under mild conditions with a yield of about 50%.

[0020] Amberger et al. (Zeitschrift fuer Naturforschung 1963, 18b 157) also disclosed the preparation and properties of trimethylsilyl thiocyanate, which was produced by reacting Li3Sb + SiH3Br in ether at low temperature, followed by photoisolation to generate 77% Sb(SiH3)3.

[0021] Drake et al. (J. Chem. Soc., 1969, 662-665) disclosed the synthesis of P(Si2)3 by reacting an appropriate amount of diborane with Si2-PH2: 3SiH3SiH2PH2 → (promoted by B2H6)P(Si2H5)3 + 2PH3.

[0022] Drake et al. (Inorg. Chem. [Inorganic Chemistry], 1967, 6(11). 1984-1986; Chem. Ind. [Chemistry and Industry], 1962, 1470) disclosed the synthesis and purification of monosilylphosphine such as SiH3SiH2-PH2 by inducing the decomposition of a mixture of silane and phosphine in a silent discharge of an ozone generator, followed by trap-to-trap distillation.

[0023] Drake et al. (J. Chem. Soc. A., 1968, 2709) disclosed the formation of (GeH3)3P by disproportionation of GeH3PH2.

[0024] Drake et al. (J. Chem. Soc. A, 1971, 13, 2246) disclosed that the reaction between P(SiH3)3 and LiAlH4 will produce one of the products, such as LiAlH[P(SiH3)2]3 + Si2H5Br → Si2H5-P(SiH3)2.

[0025] Drake et al. (Inorg. Nucl. Chem. Letters, 1968, Vol. 4, pp. 361-363) disclosed that monobromogerane reacts with trimethylsilylphosphine to produce an "exchange," resulting in the formation of trigermylphosphine. Monobromosilane reacts with KMH2 (M = P, As, Sb) to yield trimethylsilyl rather than monomethylsilyl derivatives, and monoiodosilane reacts with dimethylsilylamine to yield trimethylsilyl substances.

[0026] Cradock et al. (J. Chem. Soc. A., 1967, 1229) disclosed an exchange reaction from GeH3Br-(SiH3)3P to (GeH3)3P.

[0027] Wingeleth et al. (Phosphorus and Sulfur and the related Elements, 1988, 39, 123-9) disclosed the formation of P(SiH3)3, P(Si2H5)3, P(SiH3)2(Si2H5), and P(GeH3)3 through redistribution reactions of monosilylphosphine or monogermanium-based phosphine (including SiH3PH2, Si2H5PH2, SiH3PH2 / Si2H5PH2, and GeH3PH2) promoted by BX3, B2H6, and B5H9.

[0028] Beagley et al. (Chem. Commun., 1967, 12, 601-602) disclosed the gas-phase pyramid structures of P(SiH3)3 and As(SiH3)3.

[0029] Yang et al. (Chem. Mater. [Materials Chemistry] 2014, 26, 14, 4092-4101) disclosed that an Al-P(SiH3)3 intermediate containing an Al-PSi3 core was formed by a low-temperature reaction between P(SiH3)3 and an Al atomic beam. This intermediate has recently been shown to be able to be deposited and matched on a Si(100) lattice, thus providing a practical pathway for growing III-V materials on group IV semiconductors.

[0030] Watkins et al. (J. Am. Chem. Soc. [Journal of the American Chemical Society] 2011, 133, 40, 16212-16218) disclosed the preparation, characterization and theoretical simulation of tetragonal strained Al-PSi3 cores grown on Si(100).

[0031] Chizmeshya et al. (ECS Transactions, 2012, 50(9), 623-634) disclosed a similar application of forming intermediates with Al-PSi3 cores using molecular beam epitaxy (MBE) at <600°C and then incorporating them into rhombic group IV materials. Similarly, Al-AsSi3 can be deposited using As(SiH3)3 precursors and P / As, As / N, P / N hybrids by reacting mixtures of As(SiH3)3, P(SiH3)3, and N(SiH3)3 with Al to form the corresponding intermediates. This work can be extended to Al-PSi by introducing a precursor mixture of P(SiH3)3 and P(GeH3)3. 3x Ge 3(1-x) Deposition.

[0032] Sims et al. (Chem. Mater. [Materials Chemistry] 2015, 27, 8, 3030-3039) disclosed hybrids of group III materials, such as Al 1-x B x PSi3 (x = 0.04-0.06) is formed by low-P CVD processing using P(SiH3)3 and Al(BH4)3 precursors and growing on a Si-based solid.

[0033] Kouvetakis et al. (Chem. Mater. [Materials Chemistry] 2012, 24, 16, 3219-3230) disclosed the synthesis of (III-V)-(IV) alloys on Si substrates using M(SiH3)3 (M = P, As) and Al via gas-source MBE. Under appropriate conditions, adding N(SiH3)3 to the reaction mixture yields a novel hybrid material, Al(As). 1-x N x Si3 and Al(P) 1-x N x ) y Si 5-2y .

[0034] Romero et al.’s WO 2019066825 / US 20200168462 discloses the decomposition of Group V (including N, P, As, Sb, and Bi) and / or Group VI (including S, Se, and Te) materials using corresponding hydrides and / or silylated substances, including silylated phosphine, arsenic, arsenic, and bismuth.

[0035] US 7029995 by Todd et al. discloses a method for forming epitaxial films in which phosphorus, arsenic, and antimony are supplied in the form of precursors such as phosphine, trimethylsilylphosphine, arsine, trimethylsilylarsine, arsenic, and silylarsenic.

[0036] Weeks et al.’s US 9099423 discloses a doped semiconductor film and the processing of which the dopant contains phosphorus.

[0037] Todd's US filing 6716751 discloses the use of (H3Si). 3-x Silicon alloys and doped silicon films formed from Si-containing precursors of MRx, (H3Si)3N and (H3Si)4N2 by CVD and ion implantation processes, wherein R is H or D, x = 0, 1 or 2, and M is selected from the group consisting of B, P, As and Sb.

[0038] Dickson's US 4910153 discloses a formula (MX3). n M'X 4-n The deposition precursor, wherein M and M' are different Group 4A atoms, at least one of M and M' is silicon, X is hydrogen, halogen, or a mixture thereof, and n = 1 to 4, including end values. It has the formula (SiX3). m LX 3-m The dopant is L, which is a group 5A atom selected from P, As, Sb and Bi, X is hydrogen, halogen or a mixture thereof, and m is an integer between 1 and 3, including the end value.

[0039] For example, WO 2002065508 describes a formula A(SiH3). 3-x (H or D) x The application of these compounds, particularly when used in combination with a Si source, is particularly relevant when the Si source is a polysilane, such as disilane or trisilane. This chemical choice allows for film deposition at lower temperatures than the classic SiH4 / PH3 / AsH3 chemistry used in this process, and thus enables the deposition of films with dopant concentrations higher than the dopant solubility values ​​in silicon. Summary of the Invention

[0040] A method for synthesizing compounds containing group V elements is disclosed, the method comprising:

[0041] A(SiR3)3 is contacted with one, two, or three types of halo(poly)silanes in sequence or in a mixture, wherein the halo(poly)silanes are selected from the group consisting of: X-Si a H 2a+1 X-Si b H 2b+1 and X-Si c H 2c+1;as well as

[0042] A(SiR3)3 is dehalogenated and silanized as follows to form a compound containing group V elements.

[0043] (SiR3) 3-m A(Si a H 2a+1 ) m ,or

[0044] (SiR3) 3-n-p A(Si a H 2a+1 ) n (Si b H 2b+1 ) p or

[0045] A(Si a H 2a+1 (Si) b H 2b+1 (Si) c H 2c+1 )

[0046] A gradual, general response:

[0047] a) One-step reaction:

[0048] A(SiR3)3 + m X-Si a H 2a+1 → (SiR3) 3-m A(Si a H 2a+1 ) m + m X-SiR3,

[0049] b) Two-step reaction:

[0050] A(SiR3)3 + n X-Si a H 2a+1 → (SiR3) 3-n A(Si a H 2a+1 ) n + n X-SiR3

[0051] (SiR3) 3-n A(Si a H 2a+1 ) n + p X-(Si b H 2b+1 → (SiR3) 3-n-p A(Si a H 2a+1 ) n(Si b H 2b+1 ) p + pX-SiR3, or

[0052] c) Three-step reaction:

[0053] A(SiR3)3 + X-Si a H 2a+1 → (SiR3)2A(Si a H 2a+1 ) + X-SiR3

[0054] (SiR3)2A(Si a H 2a+1 ) + X-Si b H 2b+1 → (SiR3)A(Si a H 2a+1 (Si) b H 2b+1 ) + X-SiR3

[0055] (SiR3)A(Si a H 2a+1 (Si) b H 2b+1 ) + X-Si c H 2c+1 → A(Si a H 2a+1 (Si) b H 2b+1 (Si) c H 2c+1 ) +X-SiR3;

[0056] Alternatively, a one-pot reaction with a mixture of two or three halo(poly)silanes:

[0057] A(SiR3)3 + x X-Si a H 2a+1 + y X-Si b H 2b+1 + z X-Si c H 2c+1 → A(Si a H 2a+1 ) x (Si b H 2b+1 ) y (Si c H 2c+1 ) z (SiR3) (3-x-y-z) + (x + y + z) X-SiR3,

[0058] in

[0059] X = Cl, Br, or I;

[0060] a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c;

[0061] m = 1 to 3;

[0062] n = 1 to 2, p = 1 to 2, n + p = 2 to 3;

[0063] x = 0 to 3, y = 0 to 3, z = 0 to 3, x + y + z = 1 to 3;

[0064] A = elements selected from group V, namely As, P, Sb, and Bi; and

[0065] R is selected from C1 to C. 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups. The disclosed methods may include one or more of the following:

[0066] • Add solvent;

[0067] • The solvent is selected from alkanes or aromatic solvents, haloalkylsilanes or mixtures thereof;

[0068] • The ratio of solvent to A(SiR3)3 is 0-99 wt%;

[0069] • The alkane or aromatic solvent is selected from pentane, hexane, heptane, benzene, toluene, xylene, trimethylchlorosilane or mixtures thereof;

[0070] • The ratio of one or more halo(poly)silanes to A(SiR3)3 ranges from 1:99 to 99:1;

[0071] • The ratio of one or more halo(poly)silanes to A(SiR3)3 ranges from 1:20 to 20:1;

[0072] • The ratio of one or more halo(poly)silanes to A(SiR3)3 ranges from 1:5 to 5:1;

[0073] •X is Cl;

[0074] • Halosilanes are chlorosilanes;

[0075] • Chlorinated (poly)silanes are Cl-Si a H 2a+1 Cl-Si b H 2b+1and / or Cl-Si a H 2a+1 Where a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c;

[0076] • Chlorinated (poly)silanes are Cl-SiH3, Cl-Si2H5 or Cl-Si3H7;

[0077] •R is a methyl group (Me);

[0078] • Further includes

[0079] Separating the solvent and reaction products to isolate compounds containing Group V elements; and

[0080] Purify compounds containing group V elements;

[0081] • Compounds containing Group V elements must have a purity > 90%;

[0082] • Compounds containing Group V elements must have a purity > 95%;

[0083] • Compounds containing Group V elements must have a purity > 98%;

[0084] •This method is a batch process;

[0085] • The reaction is maintained at a temperature ranging from -20°C to 150°C;

[0086] • The reaction is maintained at temperatures ranging from room temperature to 100°C;

[0087] • Compounds containing Group V elements contain trimethylsilyl groups;

[0088] • Trimethylsilyl is -SiH(SiH3)2 (iso-trimethylsilyl);

[0089] • Trimethylsilyl is -SiH2-SiH2-SiH3 (neo-trimethylsilyl);

[0090] • The compound containing a Group V element is selected from P(SiH₃)₃, P(SiR₃)(SiH₃)₂, P(SiR₃)₂(SiH₃), P(SiR₃)(Si₂H₅)₂, P(SiR₃)₂(Si₂H₅), P(Si₂H₅)₃, P(SiR₃)(Si₃H₇)₂, P(SiR₃)₂(Si₃H₇), P(Si₃H₇)₃, As(SiH₃)₃, As(SiR₃)(SiH₃)₂, As(SiR₃)₂(SiH₃), As(SiR₃)(Si₂H₅)₂, As(SiR₃)₂(Si₂H₅), As(Si₂H₅)₃, As(SiR₃)(Si₃H₇)₂, As(SiR₃)₂(Si₃H₇), As(Si₃H₇)₃, Sb(SiH₃)₃, Sb(SiR₃)(SiH₃)₂, Sb(SiR₃)₂(SiH₃), Sb(SiR₃)(Si₂H₅)₂, Sb(SiR₃)₂(Si₂H₅), Sb(Si₂H₅)₃, Sb(SiR₃)(Si₃H₇)₂, Sb(SiR₃)₂(Si₃H₇), Sb(Si₃H₇) 3， P(SiR₃)(SiH₃)(Si₂H₅), P(SiR₃)(SiH₃)(Si₃H₇), P(SiH₃)₂(Si₂H₅), P(SiH₃)₂(Si₃H₇), P(SiH₃)(Si₂H₅)₂, P(SiH₃)(Si₂H₅)(Si₃H₇), P(SiH₃)(Si₃H₇)₂, P(Si₂H₅)₂(Si₃H₇), P(Si₂H₅)(Si₃H₇)₂, As(SiR₃)(SiH₃)(Si₂H₅), As(SiR₃)(SiH₃)(Si₃H₇), As(SiH₃)₂(Si₂H₅), As(SiH₃)₂(Si₃H₇), As(SiH₃)(Si₂H₅)₂, As(SiH₃)(Si₂H₅)(Si₃H₇), As(SiH₃)(Si₃H₇)₂, As(Si₂H₅)₂(Si₃H₇), As(Si₂H₅)(Si₃H₇)₂, Sb(SiR₃)(SiH₃)(Si₂H₅), Sb(SiR₃)(SiH₃)(Si₃H₇), Sb(SiH₃)₂(Si₂H₅), Sb(SiH₃)₂(Si₃H₇), Sb(SiH₃)(Si₂H₅)₂, Sb(SiH₃)(Si₂H₅)(Si₃H₇), Sb(SiH₃)(Si₃H₇)₂, Sb(Si₂H₅)₂(Si₃H₇), or Sb(Si₂H₅)(Si₃H₇)₂;

[0091] • R is selected from Me, Et, nPr, iPr, tBu, nBu, iBu or sBu;

[0092] •When R = Me, the compound containing a Group V element is selected from P(SiH₃)₃, P(TMS)(SiH₃)₂, P(TMS)₂(SiH₃), P(TMS)(Si₂H₅)₂, P(TMS)₂(Si₂H₅), P(Si₂H₅)₃, P(TMS)(Si₃H₇)₂, P(TMS)₂(Si₃H₇), P(Si₃H₇)₃, As(SiH₃)₃, As(TMS)(SiH₃)₂, As(TMS)₂(SiH₃), As(TMS)(Si₂H₅)₂, As(TMS)₂(Si₂H₅), As(Si₂H₅)₃, As(TMS)(Si₃H₇)₂, As(TMS)₂(Si₃H₇), As(Si₃H₇)₃, Sb(SiH₃)₃, Sb(TMS)(SiH₃)₂, Sb(TMS)₂(SiH₃), Sb(TMS)(Si₂H₅)₂, Sb(TMS)₂(Si₂H₅), Sb(Si₂H₅)₃, Sb(TMS)(Si₃H₇)₂, Sb(TMS)₂(Si₃H₇), Sb(Si₃H₇) 3， P(TMS)(SiH₃)(Si₂H₅), P(TMS)(SiH₃)(Si₃H₇), P(SiH₃)₂(Si₂H₅), P(SiH₃)₂(Si₃H₇), P(SiH₃)(Si₂H₅)₂, P(SiH₃)(Si₂H₅)(Si₃H₇), P(SiH₃)(Si₃H₇)₂, P(Si₂H₅)₂(Si₃H₇), P(Si₂H₅)(Si₃H₇)₂, As(TMS)(SiH₃)(Si₂H₅), As(TMS)(SiH₃)(Si₃H₇), As(SiH₃)₂(Si₂H₅), As(SiH₃)₂(Si₃H₇), As(SiH₃)(Si₂H₅)₂, As(SiH₃)(Si₂H₅)(Si₃H₇), As(SiH₃)(Si₃H₇)₂, As(Si₂H₅)₂(Si₃H₇), As(Si₂H₅)(Si₃H₇)₂, Sb(TMS)(SiH₃)(Si₂H₅), Sb(TMS)(SiH₃)(Si₃H₇), Sb(SiH₃)₂(Si₂H₅), Sb(SiH₃)₂(Si₃H₇), Sb(SiH₃)(Si₂H₅)₂, Sb(SiH₃)(Si₂H₅)(Si₃H₇), Sb(SiH₃)(Si₃H₇)₂, Sb(Si₂H₅)₂(Si₃H₇), or Sb(Si₂H₅)(Si₃H₇)₂;

[0093] • Compounds containing Group V elements are selected from the group consisting of: P(SiH3)3, P(TMS)(SiH3)2, P(TMS)2(SiH3), P(TMS)(Si2H5)2, P(TMS)2(Si2H5), P(Si2H5)3, P(TMS)(Si3H7)2, P(TMS)2(Si3H7), P(Si3H7)3, P(TMS)(SiH3)(Si2H5), P(TMS)(SiH3)(Si3H7), P(SiH3)2(Si2H5), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7) and P(Si2H5)(Si3H7)2;

[0094] • When n = 2 to 3, compounds containing group V elements are selected from the following groups: A(Si2H5)(SiR3)2, A(Si3H7)(SiR3)2, A(Si2H5)2(SiR3), A(Si3H7)2(SiR3), A(Si2H5)3, and A(Si3H7)3, where A is a group V element selected from P, As, Sb, or Bi; and R is selected from C1 to C2. 10 Straight-chain, branched, or cyclic alkyl, alkenyl, and alkynyl groups; provided that if A = P, then P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) are excluded; and

[0095] • When m = 3, the compound containing group V elements is A(Si). a H 2a+1 )3, where a = 1 to 6; A is a group V element selected from P, As, Sb or Bi; R is selected from C1 to C 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups; provided that if A = As, then a > 1; if A = P, then P(Si2H5)3 is excluded; and if A = Sb, then Sb(SiH3)3 is excluded.

[0096] A compound containing a group V element was also disclosed, which has the following formula:

[0097] (SiR3) 3-m A(Si a H 2a+1 ) m ,

[0098] (SiR3) 3-n-p A(Si a H 2a+1) n (Si b H 2b+1 ) p or

[0099] A(Si a H 2a+1 (Si) b H 2b+1 (Si) c H 2c+1 )

[0100] in

[0101] a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c;

[0102] m = 1 to 3;

[0103] n = 1 to 2, p = 1 to 2, n + p = 2 to 3;

[0104] A = elements selected from group V, namely As, P, Sb, and Bi; and

[0105] R is selected from C1 to C. 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups;

[0106] The prerequisites are: if A = As, then As(SiH3)3 is excluded; if A = P, then P(SiH3)3, P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) are excluded; and if A = Sb, then Sb(SiH3)3 is excluded. The disclosed compounds may include one or more of the following:

[0107] • Compounds containing Group V elements must have a purity > 93%;

[0108] • Compounds containing Group V elements must have a purity > 95%; and

[0109] • The purity of compounds containing Group V elements is > 98%.

[0110] A method for forming a film containing Si and group V elements on a substrate is also disclosed, the method comprising:

[0111] Exposing the substrate to the vapor of a film-forming composition containing precursors of Si and Group V elements; and

[0112] At least a portion of the precursor containing Si and Group V elements is deposited onto the substrate using a vapor phase deposition method to form a film containing Si and Group V elements on the substrate.

[0113] The precursors containing Si and group V elements have the following general formula.

[0114] (SiR3) 3-m A(Si a H 2a+1 ) m ,

[0115] (SiR3) 3-n-p A(Si a H 2a+1 ) n (Si b H 2b+1 ) p or

[0116] A(Si a H 2a+1 (Si) b H 2b+1 (Si) c H 2c+1 )

[0117] in

[0118] A is a group V element selected from P, As, Sb or Bi;

[0119] a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c;

[0120] m = 1 to 3;

[0121] n = 1 to 2, p = 1 to 2, n + p = 2 to 3;

[0122] R is selected from C1 to C. 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups;

[0123] The premise is that if A = As, then As(SiH3)3 is excluded; if A = P, then P(SiH3)3, P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) are excluded; and if A = Sb, then Sb(SiH3)3 is excluded. The disclosed method may include one or more of the following aspects:

[0124] •The Group V element-containing precursor is selected from P(SiH3)3, P(SiR3)(SiH3)2, P(SiR3)2(SiH3), P(SiR3)(Si2H5)2, P(SiR3)2(Si2H5), P(Si2H5)3, P(SiR3)(Si3H7)2, P(SiR3)2(Si3H7), P(Si3H7)3, As(SiH3)3, As(SiR3)(SiH3)2, As(SiR3)2(SiH3), As(SiR3)(Si2H5)2, As(SiR3)2(Si2H5), As(Si2H5)3, As(SiR3)(Si3H7)2, As(SiR3)2(Si3H7), As(Si3H7)3, Sb(SiH3)3, Sb(SiR3)(SiH3)2, Sb(SiR3)2(SiH3), Sb(SiR3)(Si2H5)2, Sb(SiR3)2(Si2H5), Sb(Si2H5)3, Sb(SiR3)(Si3H7)2, Sb(SiR3)2(Si3H7), Sb(Si3H7) 3， P(SiR3)(SiH3)(Si2H5), P(SiR3)(SiH3)(Si3H7), P(SiH3)2(Si2H5), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7), P(Si2H5)(Si3H7)2, As(SiR3)(SiH3)(Si2H5), As(SiR3)(SiH3)(Si3H7), As(SiH3)2(Si2H5), As(SiH3)2(Si3H7), As(SiH3)(Si2H5)2, As(SiH3)(Si2H5)(Si3H7), As(SiH3)(Si3H7)2, As(Si2H5)2(Si3H7), As(Si2H5)(Si3H7)2, Sb(SiR3)(SiH3)(Si2H5), Sb(SiR3)(SiH3)(Si3H7), Sb(SiH3)2(Si2H5), Sb(SiH3)2(Si3H7), Sb(SiH3)(Si2H5)2, Sb(SiH3)(Si2H5)(Si3H7), Sb(SiH3)(Si3H7)2, Sb(Si2H5)2(Si3H7), or Sb(Si2H5)(Si3H7)2;

[0125] •R is selected from Me, Et, nPr, iPr, tBu, nBu, iBu or sBu;

[0126] • Precursors containing Si and Group V elements are selected from P(TMS)(SiH3)2, P(TMS)2(SiH3), P(TMS)(Si2H5)2, P(TMS)2(Si2H5), P(TMS)(Si3H7)2, P(TMS)2(Si3H7), P(Si3H7)3, As(TMS)(SiH3)2, As(TMS)2(SiH3), As(TMS)(Si2H5)2, As(TMS)2(Si2H 5), As(Si2H5)3, As(TMS)(Si3H7)2, As(TMS)2(Si3H7), As(Si3H7)3, Sb(TMS)(SiH3)2, Sb(TMS)2(SiH3 ), Sb(TMS)(Si2H5)2, Sb(TMS)2(Si2H5), Sb(Si2H5)3, Sb(TMS)(Si3H7)2, Sb(TMS)2(Si3H7), Sb(Si3H7) 3， P(TMS)(SiH3)(Si2H5), P(TMS)(SiH3)(Si3H7), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7), P(Si2 H5)(Si3H7)2, As(TMS)(SiH3)(Si2H5), As(TMS)(SiH3)(Si3H7), As(SiH3)2(Si2H5), As(SiH3)2(Si3H7), As(SiH3)(Si2H5)2, As(SiH3)(Si2 H5)(Si3H7), As(SiH3)(Si3H7)2, As(Si2H5)2(Si3H7), As(Si2H5)(Si3H7)2, Sb(TMS)(SiH3)(Si2H5), Sb(TMS)(SiH3)(Si3H7), Sb(SiH3)2(S i2H5), Sb(SiH3)2(Si3H7), Sb(SiH3)(Si2H5)2, Sb(SiH3)(Si2H5)(Si3H7), Sb(SiH3)(Si3H7)2, Sb(Si2H5)2(Si3H7), or Sb(Si2H5)(Si3H7)2;

[0127] • Precursors containing Si and group V elements are selected from the following groups: P(Si3H7)3, P(SiH3)2(Si3H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7) and P(Si2H5)(Si3H7)2;

[0128] • Vapor deposition methods include CVD, ALD, epitaxial processes, or combinations thereof;

[0129] • The film-forming composition is activated by heating the substrate to a temperature ranging from 200°C to 1000°C, plasma-activating precursors containing Si and Group V elements, or combinations thereof;

[0130] • Further includes the step of exposing the substrate to the co-reactant;

[0131] • The co-reactants are plasma-activated;

[0132] • The co-reactants are not plasma-activated;

[0133] • The co-reactants are selected from O2, O 3、 H2O, H2O2, NO, N2O, NO2, O free radicals, alcohols, silanols, amino alcohols, carboxylic acids, paraformaldehyde or combinations thereof containing oxygen;

[0134] • The co-reactant is O3;

[0135] • The co-reactants are nitrogen-containing gases selected from NH3, N2, H2, N2 / H2, H2 and NH3, N2 and NH3, NH3 and N2H4, NO, N2O, amines, trimethylsilylamines, silazanes or combinations thereof;

[0136] • The co-reactant is H2;

[0137] • The co-reactant is N2;

[0138] • The co-reactant is at least one second precursor selected from silanes and polysilanes, alkylsilanes, halosilanes (MCS, DCS, TCS, SiCl4), polyhalogenated polysilanes, germananes, chlorogermananes, digermananes, polygermananes, halogermananes, phosphine, boranes or halogenated gases.

[0139] • The co-reactant is a dilution gas selected from Ar, He, N2, H2 or a combination thereof;

[0140] • Films containing Si and Group V elements are P-doped silicon-containing films;

[0141] • Further includes the step of annealing the Si and Group V elements-containing layer by thermal annealing, in-furnace annealing, rapid thermal annealing, UV or electron beam curing and / or plasma gas exposure;

[0142] • The substrate is powder; and

[0143] • The powder contains one or more of NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials.

[0144] A film-forming composition for depositing films is also disclosed, comprising a precursor containing Si and group V elements, the precursor having the following formula:

[0145] (SiR3) 3-m A(Si a H 2a+1 ) m ,

[0146] (SiR3) 3-n-p A(Si a H 2a+1 ) n (Si b H 2b+1 ) p or

[0147] A(Si a H 2a+1 (Si) b H 2b+1 (Si) c H 2c+1 )

[0148] in

[0149] A is a group V element selected from P, As, Sb or Bi;

[0150] a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c;

[0151] m = 1 to 3;

[0152] n = 1 to 2, p = 1 to 2, n + p = 2 to 3;

[0153] R is selected from C1 to C. 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups;

[0154] The prerequisites are: if A = As, then As(SiH3)3 is excluded; if A = P, then P(SiH3)3, P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) are excluded; and if A = Sb, then Sb(SiH3)3 is excluded. The disclosed film-forming compositions include one or more of the following:

[0155] • The precursor containing a Group V element is selected from P(SiH₃)₃, P(SiR₃)(SiH₃)₂, P(SiR₃)₂(SiH₃), P(SiR₃)(Si₂H₅)₂, P(SiR₃)₂(Si₂H₅), P(Si₂H₅)₃, P(SiR₃)(Si₃H₇)₂, P(SiR₃)₂(Si₃H₇), P(Si₃H₇)₃, As(SiH₃)₃, As(SiR₃)(SiH₃)₂, As(SiR₃)₂(SiH₃), As(SiR₃)(Si₂H₅)₂, As(SiR₃)₂(Si₂H₅), As(Si₂H₅)₃, As(SiR₃)(Si₃H₇)₂, As(SiR₃)₂(Si₃H₇), As(Si₃H₇)₃, Sb(SiH₃)₃, Sb(SiR₃)(SiH₃)₂, Sb(SiR₃)₂(SiH₃), Sb(SiR₃)(Si₂H₅)₂, Sb(SiR₃)₂(Si₂H₅), Sb(Si₂H₅)₃, Sb(SiR₃)(Si₃H₇)₂, Sb(SiR₃)₂(Si₃H₇), Sb(Si₃H₇) 3， P(SiR₃)(SiH₃)(Si₂H₅), P(SiR₃)(SiH₃)(Si₃H₇), P(SiH₃)₂(Si₂H₅), P(SiH₃)₂(Si₃H₇), P(SiH₃)(Si₂H₅)₂, P(SiH₃)(Si₂H₅)(Si₃H₇), P(SiH₃)(Si₃H₇)₂, P(Si₂H₅)₂(Si₃H₇), P(Si₂H₅)(Si₃H₇)₂, As(SiR₃)(SiH₃)(Si₂H₅), As(SiR₃)(SiH₃)(Si₃H₇), As(SiH₃)₂(Si₂H₅), As(SiH₃)₂(Si₃H₇), As(SiH₃)(Si₂H₅)₂, As(SiH₃)(Si₂H₅)(Si₃H₇), As(SiH₃)(Si₃H₇)₂, As(Si₂H₅)₂(Si₃H₇), As(Si₂H₅)(Si₃H₇)₂, Sb(SiR₃)(SiH₃)(Si₂H₅), Sb(SiR₃)(SiH₃)(Si₃H₇), Sb(SiH₃)₂(Si₂H₅), Sb(SiH₃)₂(Si₃H₇), Sb(SiH₃)(Si₂H₅)₂, Sb(SiH₃)(Si₂H₅)(Si₃H₇), Sb(SiH₃)(Si₃H₇)₂, Sb(Si₂H₅)₂(Si₃H₇), or Sb(Si₂H₅)(Si₃H₇)₂;

[0156] • R is selected from Me, Et, nPr, iPr, tBu, nBu, iBu or sBu;

[0157] • When R = Me, the precursors containing Si and group V elements are selected from P(TMS)(SiH3)2, P(TMS)2(SiH3), P(TMS)(Si2H5)2, P(TMS)2(Si2H5), P(TMS)(Si3H7)2, P(TMS)2(Si3H7), P(Si3H7)3, As(TMS)(SiH3)2, As(TMS)2(SiH3), As(TMS)(Si2H5)2, As(TMS)2(Si 2H5), As(Si2H5)3, As(TMS)(Si3H7)2, As(TMS)2(Si3H7), As(Si3H7)3, Sb(TMS)(SiH3)2, Sb(TMS)2(SiH 3), Sb(TMS)(Si2H5)2, Sb(TMS)2(Si2H5), Sb(Si2H5)3, Sb(TMS)(Si3H7)2, Sb(TMS)2(Si3H7), Sb(Si3H7) 3， P(TMS)(SiH3)(Si2H5), P(TMS)(SiH3)(Si3H7), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7), P(Si2 H5)(Si3H7)2, As(TMS)(SiH3)(Si2H5), As(TMS)(SiH3)(Si3H7), As(SiH3)2(Si2H5), As(SiH3)2(Si3H7), As(SiH3)(Si2H5)2, As(SiH3)(Si2 H5)(Si3H7), As(SiH3)(Si3H7)2, As(Si2H5)2(Si3H7), As(Si2H5)(Si3H7)2, Sb(TMS)(SiH3)(Si2H5), Sb(TMS)(SiH3)(Si3H7), Sb(SiH3)2(S i2H5), Sb(SiH3)2(Si3H7), Sb(SiH3)(Si2H5)2, Sb(SiH3)(Si2H5)(Si3H7), Sb(SiH3)(Si3H7)2, Sb(Si2H5)2(Si3H7), or Sb(Si2H5)(Si3H7)2;

[0158] • The purity of precursors containing Si and Group V elements is > 93%;

[0159] • The purity of precursors containing Si and Group V elements is > 95%; and

[0160] • The purity of precursors containing Si and Group V elements is > 98%.

[0161] A wet film-forming composition for spin-coating films is also disclosed, comprising a Si- and Group V-containing precursor of formula (I), (II), or (III) having at least 5 Si atoms. The disclosed wet film-forming composition may include one or more of the following aspects:

[0162] • Select precursors containing Si and Group V elements of formula (I), (II), or (III) with the lowest volatility to be retained in the spin film and decomposed in situ during the annealing step;

[0163] • Further includes a co-reactant, which is a polysilane or a mixture of polysilanes having 5 or more silicon atoms;

[0164] • The polysilane is cyclopentalsilane;

[0165] • Polysilane is cyclohexylsilane;

[0166] • Further contains solvent;

[0167] • Spin films are amorphous or polycrystalline Si films;

[0168] • Spin films are amorphous and polycrystalline Si films;

[0169] • Spin films are amorphous Si films; and

[0170] • The spin film is a polycrystalline Si film;

[0171] A method for forming an epitaxial Si film doped with group V elements on a substrate is also disclosed, the method comprising:

[0172] The substrate is kept at or near the predetermined deposition temperature;

[0173] The substrate is exposed to a mixture of vapors from a film-forming composition and vapors from a co-reactant polysilane, the film-forming composition containing precursors containing Si and Group V elements; and

[0174] At least a portion of the precursor containing Si and group V elements is deposited onto the substrate using a CVD process to form an epitaxial Si film doped with group V elements on the substrate.

[0175] The precursors containing Si and group V elements have the following general formula.

[0176] (SiR3) 3-m A(Si a H 2a+1 ) m ,

[0177] (SiR3) 3-n-p A(Si a H 2a+1 )n (Si b H 2b+1 ) p or

[0178] A(Si a H 2a+1 (Si) b H 2b+1 (Si) c H 2c+1 )

[0179] in

[0180] A is a group V element selected from P, As, Sb or Bi;

[0181] a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c;

[0182] m = 1 to 3;

[0183] n = 1 to 2, p = 1 to 2, n + p = 2 to 3;

[0184] R is selected from C1 to C. 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups;

[0185] The premise is that if A = As, then As(SiH3)3 is excluded; if A = P, then P(SiH3)3, P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) are excluded; and if A = Sb, then Sb(SiH3)3 is excluded. The disclosed method may include one or more of the following aspects:

[0186] • The mixture contains a diluent gas selected from Ar, He, N2, H2 or combinations thereof;

[0187] • The co-reactant polysilane is germane;

[0188] • The predetermined temperature range is from 200°C to 1000°C;

[0189] • Deposition temperature range from 200°C to 1000°C; and

[0190] • When A is P, the epitaxial Si film doped with group V elements is a P-doped epitaxial Si film.

[0191] Symbols and nomenclature

[0192] The following detailed description and claims utilize many abbreviations, symbols, and terms commonly known in the art. Although definitions are typically provided first for each abbreviation, such as stainless steel (SS), certain abbreviations, symbols, and terms are used throughout the following description and claims and include the following items.

[0193] The following detailed description and claims utilize many abbreviations, symbols and terms commonly known in the art.

[0194] As used in this article, the indefinite article “a or an” means one or more or more.

[0195] As used herein, “about” or “around / approximately” in the text or claims means ± 10% of the value.

[0196] As used herein, “room temperature” in the text or claims means from about 20°C to about 25°C.

[0197] As used herein, “atmospheric pressure” in the text or claims means approximately 1 atm.

[0198] The term "substrate" refers to one or more materials on which processes are performed. A substrate can refer to a wafer having one or more materials on which processes are performed. A substrate can be any suitable wafer used in the manufacture of semiconductor, photovoltaic, flat panel, or LCD-TFT devices. A substrate can also have one or more different material layers deposited thereon from previous manufacturing steps. For example, a wafer can include silicon layers (e.g., crystalline, amorphous, porous, etc.), silicon-containing layers (e.g., SiO2, SiN, SiON, SiCOH, etc.), metal-containing layers (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.), or combinations thereof. Furthermore, a substrate can be planar or patterned. A substrate can be an organically patterned photoresist film. The substrate may include an oxide layer used as a dielectric material in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications (e.g., ZrO2-based materials, HfO2-based materials, TiO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc.) or a nitride-based film (e.g., TaN, TiN, NbN) used as an electrode. Those skilled in the art will recognize that the terms "film" or "layer" as used herein refer to a material of a certain thickness laid or spread on a surface, and that surface may be trenches or lines. Throughout the specification and claims, the wafer and any associated layers thereon are referred to as the substrate.

[0199] The term “wafer” or “patterned wafer” refers to a wafer having a stack of films on a substrate, and at least the topmost film having morphological features that have been generated in a step prior to the deposition of an indium-containing film.

[0200] The term "aspect ratio" refers to the ratio of the height of a groove (or hole) to the width of the groove (or the diameter of the hole).

[0201] It should be noted in this document that the terms “film” and “layer” are used interchangeably. It should be understood that a film can correspond to or be associated with a layer, and a layer can refer to the film. Furthermore, those skilled in the art will recognize that, as used herein, the terms “film” or “layer” refer to a material of a certain thickness laid or spread on a surface, and that surface can range from as large as an entire wafer to as small as a trench or line.

[0202] It should be noted in this article that the terms “aperture,” “via,” “hole,” and “trench” are used interchangeably to refer to openings formed in semiconductor structures.

[0203] As used herein, the abbreviation “NAND” refers to a “Negative AND or Not AND” gate; the abbreviation “2D” refers to a 2D gate structure on a planar substrate; and the abbreviation “3D” refers to a 3D or vertical gate structure in which the gate structures are stacked in the vertical direction.

[0204] It should be noted in this document that the terms "deposition temperature" and "substrate temperature" are used interchangeably. It should be understood that substrate temperature can correspond to or be related to deposition temperature, and deposition temperature can refer to substrate temperature.

[0205] It should be noted in this document that when the precursor is in a gaseous state at room temperature and ambient pressure, the terms "precursor," "deposited compound," and "deposited gas" are used interchangeably. It should be understood that a precursor can correspond to, or be associated with, a deposited compound or deposited gas, and a deposited compound or deposited gas can refer to a precursor.

[0206] This article uses the standard abbreviations of the elements in the periodic table. It should be understood that elements may be referred to by these abbreviations (for example, Si refers to silicon, N refers to nitrogen, O refers to oxygen, C refers to carbon, H refers to hydrogen, and Hal refers to halogens (F, Cl, Br, I)).

[0207] A unique CAS registry number (i.e., "CAS") assigned by the Chemical Abstracts Service is provided to identify the specific molecule disclosed.

[0208] As used herein, the term "hydrocarbon" refers to a saturated or unsaturated functional group containing only carbon and hydrogen atoms.

[0209] Please note that silicon-containing films, such as SiN and SiO, are listed throughout this specification and claims without mentioning their proper stoichiometry. Silicon-containing films may include pure silicon (Si) layers, such as crystalline Si, polycrystalline silicon (p-Si or polycrystalline Si), or amorphous silicon; silicon nitride (SiO2)... k N l ) layer; or silicon dioxide (Si) n O m A layer; or a mixture thereof, wherein k, I, m, and n range from 0.1 to 6 (inclusive of the endpoints). Preferably, silicon nitride is Si. k N l Where k and I each range from 0.5 to 1.5. More preferably, silicon nitride is Si3N4. In this document, SiN as described below can be used to represent Si-containing silicon. k N l The layer. Preferably, the silicon oxide is Si. n O m Where n ranges from 0.5 to 1.5 and m ranges from 1.5 to 3.5. More preferably, the silicon oxide is SiO2. In this document, SiO as described below can be used to represent Si-containing... n O m The silicon-containing film can also be a silicon oxide-based dielectric material, such as an organic-based or silicon oxide-based low-k dielectric material, such as Applied Materials, Inc.'s BlackDiamond II or III materials (with the formula SiOCH). The silicon-containing film may also include Si... a O b N c Where a, b, and c range from 0.1 to 6. The silicon-containing film may also include dopants from Groups III, IV, V, and VI, such as B, C, P, As, and / or Ge.

[0210] Please note that the deposited films or layers (such as silicon oxide or silicon nitride) may be enumerated throughout the specification and claims without specifying their appropriate stoichiometry (i.e., SiO, SiO2, Si3N4). These layers may include pure (Si) layers, carbide (SiO2) layers, etc. o C p ) layer, nitride (Si k N l ) layer, oxide (Si) n O m A layer or mixture thereof, wherein k, l, m, n, o, and p range from 1 to 6 (inclusive of the endpoints). For example, silicon oxide is Si. n Om Where n ranges from 0.5 to 1.5 and m ranges from 1.5 to 3.5. More preferably, the silicon oxide layer is SiO or SiO2. The silicon oxide layer can be a silicon oxide-based dielectric material, such as an organic-based or silicon oxide-based low-k dielectric material, such as Applied Materials, Inc.'s Black Diamond II or III materials. Alternatively, any reference silicon-containing layer can be pure silicon. Any silicon-containing layer may also include dopants such as B, C, P, As, and / or Ge.

[0211] As used herein, the abbreviation “Me” refers to methyl; the abbreviation “Et” refers to ethyl; the abbreviation “Pr” refers to any propyl (i.e., n-propyl or isopropyl); the abbreviation “iPr” refers to isopropyl; the abbreviation “Bu” refers to any butyl (n-butyl, isobutyl, tert-butyl, sec-butyl); the abbreviation “tBu” refers to tert-butyl; the abbreviation “sBu” refers to sec-butyl; the abbreviation “iBu” refers to isobutyl; the abbreviation “Ph” refers to phenyl; the abbreviation “Am” refers to any pentyl (isopentyl, sec-pentyl, tert-pentyl); the abbreviation “Cy” refers to a cyclic hydrocarbon group (cyclobutyl, cyclopentyl, cyclohexyl, etc.); the abbreviation “Ar” refers to an aromatic hydrocarbon group (phenyl, xylyl, mesityl, etc.); and TMS refers to trimethylsilyl-SiMe3 group.

[0212] In this document, a range may be expressed as from about one specific value and / or to about another specific value. When such a range is expressed, it should be understood that another embodiment is from one specific value and / or to another specific value, together with all combinations within the range. Any and all ranges described herein include their endpoints (i.e., x = 1 to 4 or x in the range from 1 to 4 includes x = 1, x = 4, and x = any value therebetween), whether or not the term "including endpoints" is used.

[0213] In this document, references to "an embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described with respect to that embodiment may be included in at least one embodiment of the invention. The phrase "in an embodiment" appearing in different places in the specification does not necessarily refer to the same embodiment in all instances, and individual or alternative embodiments are not necessarily mutually exclusive with other embodiments. The foregoing also applies to the term "implementation".

[0214] As used herein, the term “exemplary” is used to mean serving as an instance, example, or illustration. Any aspect or design described herein as “exemplary” is not necessarily to be construed as superior to or advantageous to other aspects or designs. Rather, the use of the term “exemplary” is intended to describe the concept in a concrete manner.

[0215] Furthermore, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". That is, unless otherwise stated or clearly indicated from the context, "X adopts A or B" is intended to mean any natural inclusive arrangement. That is, if X adopts A; X adopts B; or X adopts both A and B, then "X adopts A or B" is satisfied in any of the foregoing cases. In addition, the article "a / an" as used in this application and the appended claims should generally be interpreted as meaning "a / an or a plurality of / multiples" unless otherwise stated or clearly indicated from the context. Attached Figure Description

[0216] A fuller understanding of the foregoing and other aspects, features, and advantages of the invention, as well as the invention itself, can be obtained by referring to the following detailed description of the invention and considering it in conjunction with the accompanying drawings. The drawings are presented for illustrative purposes only and are not intended to limit the invention, wherein:

[0217] Figure 1 This is a GC chromatogram of the reaction mixture of P(TMS)3 + 7 MCTS (monochlorotrisilane, i.e., Si3H7Cl) in hexane at 68°C for 24 hours (Example 2).

[0218] Figure 2 This is a GC chromatogram of the reaction mixture of P(TMS)3 + 3 MCS (monochlorosilane, i.e. SiH3Cl) at 90°C for 44 hours (Example 4).

[0219] Figure 3 Here is a GC chromatogram of the reaction mixture of As(TMS)3 + 6 MCTS reacted at 60°C for 24 hours (Example 5); and

[0220] Figure 4 This is a GC chromatogram of the reaction mixture of Sb(TMS)3 + 10 MCS at 60°C for 24 hours (Example 8). Detailed Implementation

[0221] Disclosed are film-forming compositions containing group V elements, comprising group V element precursors containing inorganic silyl and polysilyl groups, methods for synthesizing these film-forming compositions, and methods for depositing group V element-containing films using these film-forming compositions.

[0222] The disclosed precursors containing group V elements have the following general formula:

[0223] (SiR3) 3-m A(Si a H 2a+1 ) m (I)

[0224] (SiR3)3-n-p A(Si a H 2a+1 ) n (Si b H 2b+1 ) p (II)

[0225] A(Si a H 2a+1 (Si) b H 2b+1 (Si) c H 2c+1 (III)

[0226] Where A is a group V element selected from P, As, Sb or Bi;

[0227] a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c;

[0228] m = 1 to 3;

[0229] n = 1 to 2, p = 1 to 2, n + p = 2 to 3; and

[0230] R is selected from C1 to C. 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups;

[0231] The premise is that if A = As, then As(SiH3)3 is excluded; if A = P, then P(SiH3)3, P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3 and P(SiH3)2(TMS) are excluded; and if A = Sb, then Sb(SiH3)3 is excluded.

[0232] The disclosed precursor containing group V elements contains trimethylsilyl groups, which can be -SiH(SiH3)2 (isotrimethylsilyl) or -SiH2-SiH2-SiH3 (neotrimethylsilyl).

[0233] Exemplary disclosed precursors include P(SiH₃)₃, P(SiR₃)(SiH₃)₂, P(SiR₃)₂(SiH₃), P(SiR₃)(Si₂H₅)₂, P(SiR₃)₂(Si₂H₅), P(Si₂H₅)₃, P(SiR₃)(Si₃H₇)₂, P(SiR₃)₂(Si₃H₇), P(Si₃H₇)₃, As(SiH₃)₃, As(SiR₃)(SiH₃)₂, As(SiR₃)₂(SiH₃), As(SiR₃)(Si₂H₅)₂, As(SiR₃)₂(Si₂H₅), As(Si₂H₅)₃, As(SiR₃)(Si₃H₇)₂, As(SiR₃)₂(Si₃H₇), As(Si₃H₇)₃, Sb(SiH₃)₃, Sb(SiR₃)(SiH₃)₂, Sb(SiR₃)₂(SiH₃), Sb(SiR₃)(Si₂H₅)₂, Sb(SiR₃)₂(Si₂H₅), Sb(Si₂H₅)₃, Sb(SiR₃)(Si₃H₇)₂, Sb(SiR₃)₂(Si₃H₇), Sb(Si₃H₇) 3， P(SiR₃)(SiH₃)(Si₂H₅), P(SiR₃)(SiH₃)(Si₃H₇), P(SiH₃)₂(Si₂H₅), P(SiH₃)₂(Si₃H₇), P(SiH₃)(Si₂H₅)₂, P(SiH₃)(Si₂H₅)(Si₃H₇), P(SiH₃)(Si₃H₇)₂, P(Si₂H₅)₂(Si₃H₇), P(Si₂H₅)(Si₃H₇)₂, As(SiR₃)(SiH₃)(Si₂H₅), As(SiR₃)(SiH₃)(Si₃H₇), As(SiH₃)₂(Si₂H₅), As(SiH₃)₂(Si₃H₇), As(SiH₃)(Si₂H₅)₂, As(SiH₃)(Si₂H₅)(Si₃H₇), As(SiH₃)(Si₃H₇)₂, As(Si₂H₅)₂(Si₃H₇), As(Si₂H₅)(Si₃H₇)₂, Sb(SiR₃)(SiH₃)(Si₂H₅), Sb(SiR₃)(SiH₃)(Si₃H₇), Sb(SiH₃)₂(Si₂H₅), Sb(SiH₃)₂(Si₃H₇), Sb(SiH₃)(Si₂H₅)₂, Sb(SiH₃)(Si₂H₅)(Si₃H₇), Sb(SiH₃)(Si₃H₇)₂, Sb(Si₂H₅)₂(Si₃H₇), or Sb(Si₂H₅)(Si₃H₇)₂, wherein R is selected from Me, Et, nPr, iPr, tBu, nBu, iBu or sBu.

[0234] Preferably, when R is methyl or -CH3, the disclosed precursor containing group V elements is A(Si). a H 2a+1 ) m (Si(CH3)3) 3-m or A(Si) n H 2n+1 ) m (TMS) 3-mWhere a = 1 to 6; m = 1 to 3; A is a group V element selected from P, As, Sb, or Bi; provided that if A = As, then a > 1; if A = P, then P(SiH3)2(TMS) is excluded; and if A = Sb, then Sb(SiH3)3 is excluded. When R = In the case of Me, the disclosed precursors include, for example, P(SiH3)3, P(TMS)(SiH3)2, P(TMS)2(SiH3), P(TMS)(Si2H5)2, P(TMS)2(Si2H5), P(Si2H5)3, P(TMS)(Si3H7)2, P(TMS)2(Si3H7), P(Si3H7)3, As(SiH3)3, As(TMS)(SiH3)2, As(TMS)2(SiH3), As(TMS)(Si2H5)2, As(TMS)2(Si2H5), As(Si2H5)3, As(T MS)(Si3H7)2, As(TMS)2(Si3H7), As(Si3H7)3, Sb(SiH3)3, Sb(TMS)(SiH3)2, Sb(TMS)2(SiH3), Sb(TMS)(Si2H5)2, Sb(TMS)2(Si2H5) , Sb(Si2H5)3, Sb(TMS)(Si3H7)2, Sb(TMS)2(Si3H7), Sb(Si3H7)3, P(TMS)(SiH3)(Si2H5), P(TMS)(SiH3)(Si3H7), P(SiH3)2(Si2H5), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7), P(Si2H5)(Si3H7)2, As(TMS )(SiH3)(Si2H5), As(TMS)(SiH3)(Si3H7), As(SiH3)2(Si2H5), As(SiH3)2(Si3H7), As(SiH3)(Si2H5)2, As(SiH3)(Si2H5)(Si3H7), A s(SiH3)(Si3H7)2, As(Si2H5)2(Si3H7), As(Si2H5)(Si3H7)2, Sb(TMS)(SiH3)(Si2H5), Sb(TMS)(SiH3)(Si3H7), Sb(SiH3)2(Si2H5) , Sb(SiH3)2(Si3H7), Sb(SiH3)(Si2H5)2, Sb(SiH3)(Si2H5)(Si3H7), Sb(SiH3)(Si3H7)2, Sb(Si2H5)2(Si3H7), Sb(Si2H5)(Si3H7)2.

[0235] Preferably, when n = 2 to 3, the disclosed group V element-containing precursor is selected from the group consisting of: A(Si2H5)(SiR3)2, A(Si3H7)(SiR3)2, A(Si2H5)2(SiR3), A(Si3H7)2(SiR3), A(Si2H5)3 and A(Si3H7)3, wherein A is a group V element selected from P, As, Sb or Bi; and R is selected from C1 to C2. 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups; provided that if A = P, then P(SiH3)2(Si2H5) and P(SiH3)(Si2H5) are excluded. 2， P(Si2H5)3 and P(SiH3)2(TMS).

[0236] Preferably, when m = 3, the disclosed precursor containing group V elements is A(Si). a H 2a+1 )3, where a = 1 to 6; A is a group V element selected from P, As, Sb or Bi; R is selected from C1 to C 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups; provided that if A = As, then n > 1; if A = P, then P(Si2H5)3 is excluded; and if A = Sb, then Sb(SiH3)3 is excluded.

[0237] The disclosed precursors containing group V elements can be P(SiH3)3, P(TMS)(SiH3)2, P(TMS)2(SiH3), P(TMS)(Si2H5)2, P(TMS)2(Si2H5), P(Si2H5)3, P(TMS)(Si3H7)2, P(TMS)2(Si3H7), P(Si3H7)3, P(TMS)(SiH3)(Si2H5), P(TMS)(SiH3)(Si3H7), P(SiH3)2(Si2H5), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7), or P(Si2H5)(Si3H7)2.

[0238] The disclosed methods for synthesizing the group V-containing precursors shown in formulas (I) to (III) include halosilyl or halopolysilyl compounds (X-Si n H 2n+1The dehalogenation silanization (DXS) pathway between A (SiR3)3 and tri(trialkylsilyl) derivatives of A (A = As, P, Sb or Bi) is based on the following general reaction:

[0239] A(SiR3)3 + m X-Si a H 2a+1 → A(Si a H 2a+1 ) m (SiR3) 3-m + m X-SiR3(IV)

[0240] Where a = 1 to 6;

[0241] m = 1 to 3, with m = 3 being preferred;

[0242] A = As, P, Sb, Bi;

[0243] X = Cl, Br, I; and

[0244] R is selected from C1 to C. 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups.

[0245] The disclosed synthesis method includes the following steps: reacting A(SiR3)3 with a halo(poly)silane (X-Si a H 2a+1 Optionally, the reaction is carried out with the addition of a solvent, wherein the ratio of the halo(poly)silane to A(SiR3)3 ranges from 1:100 equivalents to 100:1 equivalents, preferably from 1:20 equivalents to 20:1 equivalents, and preferably, the halo(poly)silane is a chloro(poly)silane. The solvent is used to react the two reactants A(SiR3)3 and the halo(poly)silane (X-Si... a H 2a+1The solvent is inert, selected from alkanes or aromatic solvents such as pentane, hexane, heptane, benzene, toluene, xylene, etc., or haloalkylsilanes, or mixtures thereof, and is 0-99 wt% relative to the reactants or starting materials such as A(SiR3)3. The optimal ratio of halo(poly)silane to A(SiR3)3 can be optimized to achieve the target precursor with the highest yield. For reactions (VI) where a = 1 or 2, pure monochlorosilane (MCS, ClSiH3) or monochlorodisilane (MCDS, ClSiH2SiH3) in solvent can be added via a sealed manifold by direct liquid addition or pure vapor condensation. The mixture of reactants is then stirred for a period of time, typically 1 to 168 hours, to form a reaction mixture. The product can then be separated from the reaction mixture by solvent stripping and / or fractionation or other suitable means known in the art. The separated product can then be purified, for example, by batch or continuous distillation, to achieve the desired product purity.

[0246] Here, the ratio of halo(poly)silane to A(SiR3)3 ranges from 1:99 to 99:1, preferably from 1:20 to 20:1, more preferably from 1:10 to 10:1, and even more preferably from 1:5 to 5:1. The reaction is maintained at a temperature ranging from -20°C to 150°C, preferably from room temperature to 100°C. The synthesis time span ranges from 1 to 168 hours, preferably from 12 to 96 hours, more preferably from 24 to 48 hours, depending on the reaction conditions, such as the reaction temperature.

[0247] Alternatively, the disclosed synthetic method can be carried out stepwise, and silanes of various sizes can be sequentially substituted as in a two- or three-step reaction.

[0248] The disclosed two-step reaction of a halosilyl or halopolysilyl compound with a tri(trialkylsilyl) derivative of A has the following general reaction:

[0249] A(SiR3)3 + n X-Si a H 2a+1 → (SiR3) 3-n A(Si a H 2a+1 ) n + n X-SiR3(V)

[0250] (SiR3) 3-n A(Si a H 2a+1 ) n + p X-(Si b H 2b+1 ) → A(Si a H2a+1 ) 3-n-p (Si b H 2b+1 ) p + p X-SiR3,(VI)

[0251] Where a = 1 to 6, b = 1 to 6;

[0252] n = 1 to 2, p = 1 to 2, n + p = 2 to 3;

[0253] A = As, P, Sb, Bi;

[0254] X = Cl, Br, I; and

[0255] R is selected from C1 to C. 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups.

[0256] The disclosed three-step reaction of a tri(trialkylsilyl) derivative of A with a halosilyl or halopolysilyl group has the following general reaction:

[0257] A(SiR3)3 + X-Si a H 2a+1 → (SiR3)2A(Si a H 2a+1 ) + X-SiR3(VII)

[0258] (SiR3)2A(Si a H 2a+1 ) + X-Si b H 2b+1 → (SiR3)A(Si a H 2a+1 (Si) b H 2b+1 ) + X-SiR3(VIII)

[0259] (SiR3)A(Si a H 2a+1 (Si) b H 2b+1 ) + X-Si c H 2c+1 → A(Si a H 2a+1 (Si) b H 2b+1 (Si) c H 2c+1 +X-SiR3 (IX)

[0260] Where a = 1 to 6, b = 1 to 6, c = 1 to 6;

[0261] A = As, P, Sb, Bi;

[0262] X = Cl, Br, I; and

[0263] R is selected from C1 to C. 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups.

[0264] Alternatively, the disclosed synthesis method can be carried out in a mixture or in a one-pot process, and silanes of various sizes can be substituted in a mixture of all starting materials.

[0265] The disclosed mixed reaction of halosilyl or halopolysilyl with a tris(trialkylsilyl) derivative of A has the following general reaction:

[0266] A(SiR3)3 + x X-Si a H 2a+1 + y X-Si b H 2b+1 + z X-Si c H 2c+1 → A(Si a H 2a+1 ) x (Si b H 2b+1 ) y (Si c H 2c+1 ) z (SiR3) (3-x-y-z) + (x + y + z) X-SiR3(X)

[0267] Where a = 1 to 6, b = 1 to 6, c = 1 to 6;

[0268] x = 0 to 3, y = 0 to 3, z = 0 to 3, x + y + z = 1 to 3;

[0269] A = As, P, Sb, Bi;

[0270] X = Cl, Br, I; and

[0271] R is selected from C1 to C. 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups.

[0272] In one embodiment, the disclosed method for synthesizing the group V-containing precursors shown in formulas (IV) to (X) is a chlorosilyl compound Cl-Si a H 2a+1 Cl-Si b H 2b+1 and / or Cl-Si a H 2a+1 With A (A = As, P, Sb or Bi) tri(trialkylsilyl) derivatives, A(SiR3)3 (R selected from C1 to C2) 10 Dechlorosilylation (DCS) pathway between straight-chain, branched, or cyclic alkyl, alkenyl, and alkynyl groups.

[0273] The disclosed synthetic reaction can be carried out in batch mode. In this case, A(SiR3)3 can be added to a halo(poly)silane (e.g., a chloro(poly)silane) or vice versa. When it is only desired to partially replace the -SiR3 group on A, it is preferable to add a halo(poly)silane to A(SiR3)3.

[0274] The disclosed synthetic reaction can be carried out in a continuous mode, in which the streams of reactants are continuously fed and reacted. A continuous mixing system can be used to aid in contact with the reactants. The reaction may not produce any solid byproducts; however, a filtration step can be added after synthesis to remove potential solid byproducts, just in case. One or more volatile byproducts of the reaction can be continuously removed to drive the reaction toward completion or toward multi-step conversion. This is a unique advantage of the disclosed synthetic method, which produces few or no solid byproducts. It should be understood that replacing chloro(poly)silanes with brominated (poly)silanes does not significantly deviate the reaction. Chlorinated silanes are more convenient due to their availability.

[0275] The disclosed synthesis method has the following unique advantages.

[0276] • Easily available starting materials: Existing synthetic methods use reactants such as KPH2 and P(SnMe3)3, which are not readily available commercially or require fresh preparation. In contrast, the disclosed synthetic methods use P(TMS)3, As(TMS)3, or Sb(TMS)3 as starting materials, which are commercially available in large quantities with high purity.

[0277] • Chlorosilanes are also more readily available than their Br counterparts. SiH3Cl (MCS) is available as a commercial product. For example, Si2H5Cl (MCDS) and Si3H7Cl (MCTS) can be synthesized according to Cradock et al. (J. Chem. Soc. [Journal of the British Chemical Society] Dalton Trans. [Dalton Journal], 1975, 1624-1628).

[0278] • If only one type of polysilyl group is introduced, the disclosed synthetic method can be a one-step synthesis. Most existing synthetic methods are multi-step reactions involving mono- or di-silylphosphine, arsine, etc., such as SiH3PH2, Si2H5PH2, and LiAlH[P(SiH3)2]3, requiring preparation in one or more first steps followed by separation. In contrast, the disclosed synthetic method is a one-step, one-reactor process, and byproduct separation is not necessarily required during the synthesis.

[0279] • The disclosed synthetic method features mild reaction conditions. Due to the instability of the starting materials, most existing synthetic methods require the reaction to be carried out at low temperatures and with appropriate control of the reactant addition rate and / or the thawing rate of the mixture. In contrast, the disclosed synthetic method is carried out at ambient temperature to slightly elevated temperatures, such as temperatures ranging from room temperature to 100°C.

[0280] • The disclosed synthetic method has fewer side reactions and higher yields. The disclosed DHS route offers relatively high yields due to fewer side reactions, which is beneficial for subsequent separation and purification processes.

[0281] • The disclosed synthetic methods produce little or no salt formation, which is known to favor the decomposition of similar molecules, such as N-based analogs with a trimethylsilylamine (TSA) backbone.

[0282] The disclosed group V element-containing film-forming precursor, synthesized by the disclosed synthesis method, can be used to deposit Si films containing group V element dopants in silicon via vapor deposition using methods such as CVD, PECVD, ALD, PEALD, flowable CVD, HW-CVD, and epitaxy.

[0283] P and As compounds, especially their inorganic derivatives, such as As(Si) x H y 3. P(Si) x H y 3 (where x and y at each silyl moiety can be the same or different, and y = 2x + 1) can be conveniently used as a dopant in silicon. In some applications, it is strongly necessary to dope beyond the solubility limit of the dopant in silicon, for example, to reduce contact resistance in semiconductor devices. This is because polysilanes and trisilanes are capable of depositing silicon (e.g., amorphous or crystalline silicon) at temperatures below approximately 450°C at a faster rate than silanes. The disclosed precursors containing group V elements with polysilyl ligands instead of silyl ligands will also result in deposition at lower temperatures and promote dopant inclusion.

[0284] The disclosed Group V-containing precursor is provided in a high-purity container, typically made of stainless steel, carbon steel, or aluminum, which has been pre-dried to <100 ppb H₂O residue and may optionally be passivated to limit the decomposition of the precursor therein over time. The passivation process typically involves exposing the high-purity container to a silylating agent, in which case the silylating agent may be the target precursor itself, or a silane or polysilane.

[0285] The purity of the disclosed Group V-containing precursor is preferably greater than 90% w / w (i.e., 93.0% w / w to 100.0% w / w), more preferably greater than 95% w / w (i.e., 98.0% w / w to 100.0% w / w), and even more preferably greater than 98% w / w (i.e., 99.0% w / w to about 99.999% w / w or 99.0% w / w to 100.0% w / w), wherein metallic impurities are in the ppb range and oxygen-containing impurities are in the ppm to sub-ppm range, consistent with other molecules used in similar applications. The total amount of impurities is preferably less than 5% w / w (i.e., 0.0% w / w to 5.0% w / w), preferably less than 2% w / w (i.e., 0.0% w / w to 2.0% w / w), and even more preferably less than 1% w / w (i.e., 0.0% w / w to 1.0% w / w). The disclosed group V-containing precursors can be purified by recrystallization, sublimation, distillation, and / or by passing the gas or liquid through a suitable adsorbent (such as a molecular sieve).

[0286] The disclosed Group V-containing precursors may be provided in pure form or as a mixture with suitable solvents such as ethylbenzene, xylene, mesitylene, naphthane, decane, dodecane, or as polysilanes or haloalkylsilanes. The disclosed precursors may be present in solvents at varying concentrations.

[0287] When the vapor pressure of the precursor is typically >50 Torr, preferably >300 Torr, at a container temperature ranging from 0°C to about 150°C, the vapor of the disclosed Group V-containing precursor can be delivered to the processing chamber in pure form without the presence of a carrier gas.

[0288] For the disclosed Group V-containing precursors with low vapor pressure, the vapor of the disclosed Group V-containing precursor is supplied to the processing chamber along with a carrier gas in a bubbler, vapor extractor, or direct liquid injection system. The carrier gas may include, but is not limited to, Ar, He, N2, H2, or combinations thereof. Bubbling with a carrier gas also removes any dissolved oxygen present in the precursor. The carrier gas and precursor are then introduced as vapor into the processing chamber. The processing chamber is typically maintained at a pressure below atmospheric pressure, preferably in the range of 0.01 to 500 Torr, and more preferably in the range of 1 to 100 Torr.

[0289] If necessary, the container containing the disclosed Group V-containing precursor can be heated or cooled to a temperature that allows the precursor to have a sufficient and appropriate vapor pressure. The container can be maintained at a temperature in the range of, for example, about 0°C to about 200°C. Those skilled in the art will recognize that the container temperature can be adjusted in known ways to control the amount of vaporized precursor.

[0290] The processing chamber can be any enclosed chamber within the apparatus in which the deposition method takes place, such as, but not limited to, parallel plate reactors, cold-wall reactors, hot-wall reactors, single-wafer reactors, multi-wafer reactors, and other types of deposition systems under conditions suitable for reacting precursors and forming a deposited film. Those skilled in the art will recognize that any of these processing chambers can be used for ALD or CVD deposition processes.

[0291] The processing chamber contains one or more substrates on which a film will be deposited. A substrate is generally defined as the material on which the process is performed. The substrate can be any suitable substrate used in the manufacture of semiconductor, photovoltaic, flat panel, and LCD-TFT devices. Examples of suitable substrates include wafers such as silicon, silicon dioxide, glass, and GaAs wafers. Wafers can have one or more layers of different materials deposited thereon from previous manufacturing steps. For example, a wafer can include a dielectric layer or a 3D NAND stack. Furthermore, wafers can include silicon layers (crystalline, amorphous, porous, etc.), silicon oxide layers, silicon nitride layers, silicon oxynitride layers, carbon-doped silicon oxide (SiCOH) layers, metals, metal oxides, metal nitride layers (Ti, Ru, Ta, etc.), and combinations thereof. Additionally, wafers can include copper layers and noble metal layers (e.g., platinum, palladium, rhodium, gold). Wafers can include barrier layers such as manganese, manganese oxide, etc. Plastic layers can also be used. Layers can be planar or patterned. When forming a patterned layer on a substrate, the disclosed vapor deposition process can deposit the layer directly onto the wafer, or directly onto one or more layers on top of the wafer. The patterned layer can be an alternating layer of two specific layers, such as SiO and SiN used in 3D NAND.

[0292] The final applications of the substrate are not limited to this invention, but this technology can be particularly beneficial for substrates such as silicon wafers, glass wafers and glass panels, beads, powders and nanopowders, monolithic porous media, printed circuit boards, plastic sheets, etc. Exemplary powder substrates include powders used in rechargeable battery technology. An unlimited number of powder materials include NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials.

[0293] The temperature and pressure within the processing chamber are maintained under conditions suitable for vapor deposition (such as ALD and CVD). In other words, after the vaporized, disclosed Group V-containing precursor is introduced into the chamber, the conditions within the chamber allow at least a portion of the precursor to deposit onto the substrate to form a layer. For example, the pressure in the reactor or the deposition pressure can be maintained at approximately 10 °C, as required by the deposition parameters. -3 Between approximately 500 and 1000, preferably between 100 and 1000. -2 The temperature is between 500 Torr and 100 Torr, more preferably between about 1 Torr and 100 Torr. Similarly, the temperature in the reactor or the deposition temperature can be maintained between room temperature and about 1000°C, preferably between 200°C and 800°C. Those skilled in the art will recognize that "deposition of at least a portion of the precursor" means that some or all of the precursor reacts with the substrate and adheres to the substrate.

[0294] The optimal temperature for film growth can be controlled by adjusting the temperature of the substrate support. Apparatus for heating the substrate is known in the art. The substrate is heated to a sufficient temperature to obtain the desired film at a sufficient growth rate and with the desired physical state and composition. Non-limiting exemplary temperature ranges to which the substrate can be heated include from about 200°C to about 800°C. When using a plasma deposition process, the deposition temperature is preferably less than 500°C. Alternatively, when heat treatment is performed, the deposition temperature can range from 200°C to about 800°C.

[0295] Alternatively, the substrate can be heated to a sufficient temperature to obtain a desired deposited film with a sufficient growth rate and the desired physical state and composition. The temperature of one or more substrates can be maintained in the range of about 200°C to 1000°C, preferably between 200°C and 800°C, and more preferably between 250°C and 600°C.

[0296] More specifically, in addition to the disclosed Group V-containing precursors, other precursors or co-reactants can be introduced into the processing chamber, such as, but not limited to, H2, silanes, polysilanes (Si2 to Si6, for Si5 and Si6 being straight-chain, branched, or cyclic), alkylsilanes such as monomethylsilanes, halosilanes (Cl-SiH3, Cl2SiH2, I2-SiH2, Cl3SiH, SiCl4, etc.) and polyhalogenated polysilanes (Si2Cl6, Si2HCl5, Cl-Si2H5, etc.), germanes, chlorine, etc. Germanane, digerane, polygerane, halogenated germanane, phosphine, borane such as B2H6, diborane, halogenated gases (HCl, Cl2, HBr, etc.); nitrogen-containing gases (NH3, N2, N2 / H2, H2 and NH3, N2 and NH3, NH3 and N2H4, NO, N2O, amines, trimethylsilylamine, silazane, etc. or combinations thereof); oxygen-containing gases (O2, O3, H2O, H2O2, NO, N2O, NO2, O radicals, alcohols, silanols, amino alcohols, carboxylic acids, paraformaldehyde, etc., and combinations thereof).

[0297] In addition, a dilution gas can be added to the process, and the dilution gas is selected from Ar, He, N2, H2 or a combination thereof.

[0298] Furthermore, co-reactants can be treated with plasma to decompose precursors or reactants into their radical forms. When using plasma treatment, at least one of H2, N2, and O2 or an inert gas (He, Ar, Kr, Xe) can be used, depending on the composition of the target membrane. The plasma source can be N2 plasma, N2 / He plasma, N2 / Ar plasma, NH3 plasma, NH3 / He plasma, NH2 / AR plasma, He plasma, Ar plasma, H2 plasma, H2 / He plasma, H2 / organic amine plasma, and mixtures thereof. For example, plasma can be generated at a power ranging from about 10 W to about 1000 W, preferably from about 50 W to about 500 W. The plasma can be generated or present within the reactor itself. Alternatively, the plasma can typically be located remotely from the reactor, for example, in a remotely positioned plasma system. Those skilled in the art will recognize methods and apparatus suitable for such plasma treatment.

[0299] For example, co-reactants can be introduced into a direct plasma reactor (which generates plasma in a reaction chamber) to produce plasma-processed reactants in a processing chamber. An exemplary direct plasma reactor includes the Titan™ PECVD system manufactured by Trion Technologies. Co-reactants can be introduced and held in the processing chamber prior to plasma processing. Alternatively, plasma processing can occur simultaneously with the introduction of precursors or reactants. In-situ plasma is typically a 13.56 MHz RF inductively coupled plasma generated between a spray head and a substrate holder. Depending on whether positive ion collisions occur, the substrate and spray head can be powered electrodes. The power typically applied in the in-situ plasma generator ranges from approximately 30 W to approximately 1000 W. Preferably, power ranging from approximately 30 W to approximately 600 W is used in the disclosed method. More preferably, the power range is from approximately 100 W to approximately 500 W. The dissociation of co-reactants using in-situ plasma is typically less than that achieved using a remote plasma source for the same power input, and therefore less efficient in reactant dissociation than in remote plasma systems. This may be advantageous for depositing films on substrates that are easily damaged by plasma.

[0300] Alternatively, the co-reactants processed by plasma can be generated outside the processing chamber, for example, by a remote plasma that processes the co-reactants before they enter the processing chamber.

[0301] Vapor deposition processes can be selective or non-selective for certain surfaces.

[0302] Vapor deposition processes can be thermally driven or enhanced by plasma activation, photoactivation, microwave activation, or other suitable means to activate molecules and growth processes.

[0303] The disclosed film-forming compositions containing Group V elements can be used to deposit films using any deposition method known to those skilled in the art. Examples of suitable vapor deposition methods include CVD and ALD. Exemplary CVD methods include thermal CVD, plasma-enhanced CVD (PECVD), pulsed CVD (PCVD), low-pressure CVD (LPCVD), subatmospheric pressure CVD (SACVD), atmospheric pressure CVD (APCVD), hot-wire CVD (HWCVD, also known as cat-CVD, where the hot filament acts as the energy source for the deposition process), radical-bonded CVD, and combinations thereof. Exemplary ALD methods include thermal ALD, plasma-enhanced ALD (PEALD), spatial ALD, hot-wire ALD (HWALD), radical-bonded ALD, and combinations thereof. The deposition method is preferably hot-wall or cold-wall thermal CVD, which is capable of depositing epitaxial or amorphous films containing Si and dopant elements of the claimed compound, and optionally Ge and / or other co-dopersants.

[0304] In the ALD process, the ALD conditions within the chamber allow the disclosed group V-containing film-forming composition, adsorbed or chemisorbed onto the substrate surface, to react and form a film on the substrate. In some embodiments, the applicant believes that plasma treatment of the co-reactant can provide the energy required for the co-reactant to react with the disclosed group V-containing film-forming composition (PEALD). The co-reactant can be treated with plasma before or after introduction into the chamber.

[0305] Precursors and co-reactants containing Group V elements can be sequentially introduced into the reactor (ALD). Between the introduction of each Group V-containing precursor, any additional precursors, and co-reactants, the processing chamber can be purged with an inert gas. Another example is the continuous introduction of co-reactants and the introduction of Group V-containing precursors via pulsed introduction, while the co-reactants are sequentially activated with plasma, provided that the Group V-containing precursors and unactivated co-reactants are substantially non-reactive under the chamber temperature and pressure conditions (CW PEALD).

[0306] Each pulse of the disclosed group V-containing precursor can last from about 0.01 seconds to about 120 seconds, alternatively from about 1 second to about 80 seconds, or alternatively from about 5 seconds to about 30 seconds. Co-reactants can also be pulsed into the reactor; in such embodiments, the pulse of each co-reactant can last from about 0.01 seconds to about 120 seconds, alternatively from about 1 second to about 30 seconds, or alternatively from about 2 seconds to about 20 seconds. In another alternative, vaporized group V-containing precursors and co-reactants can be simultaneously sprayed from different portions of a spray head without mixing, while a substrate of several wafers is rotated under the spray head (space ALD).

[0307] Depending on the specific process parameters, deposition can proceed for varying durations. Typically, deposition can continue for the length necessary to produce a film with the desired properties. Depending on the specific deposition process, typical film thicknesses can range from a few angstroms to hundreds of micrometers, and typically vary from 2 to 100 nm. The deposition process can also be performed multiple times as necessary to obtain the desired film.

[0308] The disclosed Group V-containing precursors and co-reactants can be introduced into the reactor simultaneously (CVD), sequentially (ALD), or in different combinations thereof. Between the introduction of the Group V-containing precursor and the introduction of the co-reactant, the reactor can be purged with an inert gas (e.g., N2, Ar, Kr, Xe). Alternatively, the co-reactant and the Group V-containing precursor can be mixed together to form a co-reactant / compound mixture, and then introduced into the reactor as a mixture (CVD, thermal CVD, or epitaxy). Another example is the continuous introduction of the co-reactant and the introduction of the disclosed Group V-containing precursor via pulsed (pulsed CVD).

[0309] The desired film thickness can range from a molecular monolayer to 10 μm, preferably between 1 nm and 500 nm.

[0310] Depending on the co-reactants, the deposition process may contain elements other than those present in the precursors for which protection is sought, such as Ge, Ga, C, B, Sn, Al, N, O, S, Se, Te, In, Zn, Cd, and Hg.

[0311] The deposited film using the disclosed deposition method can be a p-doped film containing Si and Group V elements.

[0312] The deposited film using the disclosed deposition method can be a silicon layer doped with group V elements, such as a P-doped silicon layer.

[0313] The disclosed film-forming compositions containing Group V elements can be used for liquid-phase film deposition of Si-containing films, including but not limited to spin coating, dip coating, or spray coating. In this case, a formulation containing the disclosed compound is coated onto a substrate, which is then annealed to produce a thin film.

[0314] The disclosed film-forming compositions containing Group V elements are particularly suitable as doping components in formulations intended for the preparation of amorphous and polycrystalline Si films. Such formulations typically comprise large polysilanes or mixtures of polysilanes having > or = 5 silicon atoms (cyclopentane, cyclohexane, etc.) and a solvent. After coating a substrate with the formulation, these films are treated to produce a silicon film. For such spin-coating applications, the selected precursors should have minimal volatility to remain in the spin film and decompose in situ during the annealing step. Precursors having at least 5 Si atoms are typically suitable for such applications.

[0315] The process typically involves heating (200°C to 1000°C) and / or light / UV exposure. In such formulations, the disclosed Group V compound may be added at a rate of 0.01% to 50% (by weight) to produce a doped silicon film.

[0316] Formulations containing the disclosed Group V-containing precursors can also be used to fabricate doped silicon oxide films by surface coating followed by oxidative curing using any of the aforementioned wet coating methods. Typical oxidative curing uses at least one of H₂O (vapor), O₂, O₃, H₂O₂, and their plasmas (and optionally an inert gas), at temperatures ranging from room temperature to 1000°C. Preferably, curing comprises a two-step process: soft baking at temperatures ranging from room temperature to 250°C, and hard baking at temperatures ranging from 250°C to 1000°C. The hard baking step can be performed with or without an oxidizing gas. For these wet coating applications, it is advantageous to use completely inorganic and low-volatility precursors, preferably selected from A(Si) x H 2x+1 )3, where x is 2 or greater, and A = As or P.

[0317] Example

[0318] The following non-limiting examples are provided to further illustrate embodiments of the invention. However, these examples are not intended to include all examples, nor are they intended to limit the scope of the invention described herein.

[0319] Example 1. Synthesis of (TMS)₂P(Si₃H₇)

[0320] In a 20 mL vial, 3 g of Cl-Si3H7 MCTS was added to a solution of 11 g of P(TMS)3 (10 wt%) in hexane with magnetic stirring. The reaction mixture was stirred at room temperature under an inert atmosphere for 5 days, during which time all P(TMS)3 was converted to most of P(TMS)2(Si3H7) in 68% yield.

[0321] Example 2. Synthesis and Characterization of P(Si3H7)3

[0322] Under an inert atmosphere, 25 g of P(TMS)3 was dissolved in 200 g of anhydrous hexane in a 500 mL flask, followed by the slow addition of 75 g of monochlorotrisilane (MCTS) with magnetic stirring. The reaction mixture was refluxed at 68°C for 24 hours, during which time all P(TMS)3 was converted to P(Si3H7)3 in 93% yield. Figure 1 This is a GC chromatogram of the reaction mixture of P(TMS)3 + 7 MCTS in hexane at 68°C for 24 hours.

[0323] Example 3. Synthesis of (TMS)P(SiH3)2

[0324] 5 g of P(TMS)3 (10 wt%) from hexane was loaded into a 60 mL stainless steel container. 2.6 g of monochlorosilane MCS was cryogenically collected into the container. The reaction mixture was thawed and shaken at 150 rpm in a sealed container at 75°C for 24 hours, during which time all P(TMS)3 was converted to most of P(TMS)(SiH3)2, with a yield of 59%.

[0325] Example 4. Synthesis of P(SiH3)3

[0326] 5.6 g of P(TMS)3 was placed into a 60 mL stainless steel container. 6.9 g of monochlorosilane MCS was cryogenically collected into the container. The reaction mixture was thawed and shaken at 150 rpm in a sealed container at 90°C for 48 hours, during which time all P(TMS)3 was converted to most of P(SiH3)3, with a yield of 85%.

[0327] 235 g of P(TMS)3 was charged into a sealed 600 mL Parr reactor. 183 g of monochlorosilane MCS was cryogenically collected into the container. The reaction mixture was thawed and vigorously stirred at 400 rpm at 90°C for 44 hours, during which time all P(TMS)3 was converted to most of P(SiH3)3 in 92% yield. Figure 2 This is the GC chromatogram of the reaction mixture of P(TMS)3 + 3 MCS at 90°C for 44 hours.

[0328] Example 5. Synthesis of As(Si3H7)3

[0329] A mixture of 2 g As(TMS)3 and 7.5 g MCTS was heated at 90°C and shaken at 150 rpm for 48 hours in a 60 mL stainless steel container to produce only As(Si3H7)3 with a yield of 75%. Figure 3 The GC chromatogram of the reaction mixture of As(TMS)3 + 6 MCTS (in Example 5) at 60°C for 24 hours is shown.

[0330] Example 6. Synthesis of As(SiH3)(TMS)2

[0331] 4.5 g of As(TMS)3 was placed into a 60 mL stainless steel container. 8.5 g of monochlorosilane MCS was cryogenically collected into the container. The reaction mixture was thawed and shaken at 150 rpm at 90°C for 24 hours in a sealed container, during which most of As(SiH3)(TMS)2 was obtained, with a yield of 52%.

[0332] Example 7. Synthesis of Sb(Si3H7)(TMS)2

[0333] Sb(Si3H7)(TMS)2 can be synthesized in 72% yield by reacting 2 g of Sb(TMS)3 and 7 g of MCTS at room temperature with strong magnetic stirring for one day. High-temperature heating (e.g., 50°C or 90°C) will cause decomposition.

[0334] Example 8. Synthesis of Sb(SiH3)(TMS)2

[0335] 2.8 g of Sb(TMS)3 was placed into a 60 mL stainless steel container. 9 g of monochlorosilane MCS was cryogenically collected into the container. The reaction mixture was thawed and shaken at 150 rpm at 60°C for 24 hours in a sealed container, during which most of Sb(SiH3)(TMS)2 was obtained, with a yield of 23%. Figure 4 This is a GC chromatogram of the reaction mixture of Sb(TMS)3 + 10 MCS at 60°C for 24 hours.

[0336] Example 9. Synthesis of P(Si2H5)3

[0337] 5 g of P(TMS)3 (10 wt%) from hexane was loaded into a 60 mL stainless steel container. 2.2 g of monochlorodisilane (MCDS) was added to the container. The reaction mixture was shaken at 150 rpm at 60°C for 24 hours in a sealed container, during which P(Si2H5)3 was formed in a yield of 22%.

[0338] Example 10. Separation of P(SiH3)3

[0339] 380 g of the synthesized mixture, containing a product distribution of 26% P(SiH3)3 in TMS-Cl solution, was added to a 500 mL round-bottom flask inside a glove box. Standard fractionation was then performed. After removing volatiles at 55°C–70°C, the main fraction was collected under ambient pressure at a vapor phase temperature in the range of 115°C–125°C, yielding 75 g of P(SiH3)3 with a purity of 98%, representing a total yield of 76%. For industrial applications, further distillation or distillation with higher separation efficiency to achieve a preferred purity >99% is desirable.

[0340] Predictive Example 1: Synthesis of P(SiH3)2(Si3H7)

[0341] 10 g of 30 wt% P(TMS)(SiH3)2 in TMS-Cl (e.g., synthesized by Example 3) was placed into a 60 mL stainless steel container. 2.0 g of MCTS was added to the container. The reaction mixture was shaken at 150 rpm at 75°C for 24 hours in a sealed container, during which time P(SiH3)2(Si3H7) was formed as the major product.

[0342] Predictive Example 2: Synthesis of P(SiH3)(Si2H5)2

[0343] 118 g of P(TMS)3 was charged into a sealed 600 mL Parr reactor. 31 g of monochlorosilane MCS was cryogenically collected into the container. The reaction mixture was thawed and vigorously stirred at 400 rpm at 75°C for 24 hours, during which time all P(TMS)3 was converted to most of P(SiH3)(TMS)2.

[0344] 10 g of P(SiH3)(TMS)2, approximately 25 wt% in TMS-Cl, was placed into a 60 mL stainless steel container. 2.4 g of MCDS was added to the container. The reaction mixture was shaken at 150 rpm at 60°C for 40 hours in a sealed container, during which time P(SiH3)(Si2H5)2 was formed as the major product.

[0345] Predictive Example 3. CVD using a P-doped Si layer with precursor P(Si3H7)3

[0346] An attempt was made to deposit a P-doped Si layer on a Si(100) substrate. P(Si3H7)3 vapor was introduced into the deposition reactor (heated to approximately 500°C) at a flow rate of 10 sccm and a pressure of approximately 1–20 Torr, and carried out for 10–20 minutes, during which a polycrystalline P-doped silicon film with a thickness of 500–1500 Å was obtained. SEM images of the resulting P-doped silicon film were obtained. Elemental analysis was performed using an energy-dispersive X-ray spectroscopy (EDAX) detector. AFM, XRD, and ellipsometric measurements were performed on the resulting P-doped silicon film deposited on the Si(100) surface. Various other characterization techniques, such as atomic absorption (AA), MS-GC, NMR, FT-IR, neutron activation analysis (NAA), energy-dispersive X-ray spectroscopy (EDAX), Rutherford backscattering analysis (RBS), and X-ray analysis, were used to characterize the deposited film.

[0347] Predictive Example 4: Thermal CVD of a high-quality P-doped Si layer on a Si(100) wafer using precursor P(SiH3)2(Si3H7)

[0348] Si(100) substrates, pre-etched with diluted HF acid and appropriately conditioned (rinsed and dried), were loaded into a deposition chamber and subsequently baked with H2 at 800°C–1000°C at a flow rate of 50–120 slm. The substrate and chamber were then equilibrated at 400–600°C and a back pressure of 20–50 Torr. Pure H2 gas was then bubbled through a liquid precursor P(SiH3)2(Si3H7) to deliver the vapor of the P(SiH3)2(Si3H7) / H2 mixture into the reaction chamber at a flow rate of 50–150 sccm for 1–5 minutes. A highly crystalline P-doped epitaxial Si film with a thickness of approximately 30–150 Å was deposited on the Si(100) wafer. Hydrogen residue was confirmed to be absent by RBS.

[0349] Predictive Example 5: Thermal CVD of high-throughput P-doped Si films on Si(100) wafers using precursor P(SiH3)(Si3H7)2

[0350] Si(100) substrates, pre-etched with diluted HF acid and appropriately conditioned (rinsed and dried), were loaded into a deposition chamber and subsequently baked with H2 at 800°C–1000°C at a flow rate of 50–120 slm. The substrate and chamber were then equilibrated at approximately 550°C under a back pressure of 50 Torr. Pure H2 gas was then bubbled through a liquid precursor P(SiH3)(Si3H7)2 equilibrated at approximately 75°C and introduced into a mixing chamber at approximately 100°C via trisilane at room temperature. The vapor of the P(SiH3)(Si3H7)2 / Si3H8 / H2 mixture was then introduced into the reaction chamber at a flow rate of approximately 100 sccm for 3 minutes. A highly crystalline P-doped epitaxial Si film with a thickness of approximately 200 Å was deposited on the Si(100) wafer.

[0351] While the subject matter described herein can be described in the context of illustrative implementations to handle one or more computing application features / operations of a computing application with user interaction components, the subject matter is not limited to these specific embodiments. Rather, the techniques described herein can be applied to any suitable type of user interaction component execution management methods, systems, platforms, and / or apparatus.

[0352] It should be understood that many additional changes in details, materials, steps, and arrangements of parts that have been described and elucidated to explain the nature of the invention can be made by those skilled in the art within the principles and scope of the invention as set forth in the appended claims. Therefore, the invention is not intended to be limited to the specific embodiments given above and / or in the drawings.

[0353] Although embodiments of the invention have been shown and described, those skilled in the art can modify them without departing from the spirit or teachings of the invention. The embodiments described herein are merely exemplary and non-limiting. Many variations and modifications of the compositions and methods are possible and within the scope of the invention. Therefore, the scope of protection is not limited to the embodiments described herein, but is defined only by the following claims, the scope of which should include all equivalents of the subject matter of the claims.

Claims

1. A method for synthesizing compounds containing Group V elements, the method comprising: A(SiR3)3 is contacted with one, two, or three types of halosilanes in sequence or in a mixture, wherein the halosilanes are selected from the group consisting of: X-Si a H 2a+1 X-Si b H 2b+1 and X-Si c H 2c+1 ;as well as A(SiR3)3 is dehalogenated and silanized as follows to form this group V-containing compound. (SiR3) 3-m A(Si a H 2a+1 ) m 、 (SiR₃) 3-n-p A(Si a H 2a+1 ) n (Si b H 2b+1 ) p or A(Si a H 2a+1 )(Si b H 2b+1 )(Si c H 2c+1 ) A gradual, general response: a) One-step reaction: A(SiR3)3 + m X-Si a H 2a+1 → (SiR3) 3-m A(Si a H 2a+1 ) m + m X-SiR3, b) Two-step reaction: A(SiR3)3 + n X-Si a H 2a+1 → (SiR3) 3-n A(Si a H 2a+1 ) n + n X-SiR3 (SiR₃) 3-n A(Si a H 2a+1 ) n + p X-(Si b H 2b+1 ) → (SiR₃) 3-n-p A(Si a H 2a+1 ) n (Si b H 2b+1 ) p + p X-SiR₃, or c) Three-step reaction: A(SiR3)3 + X-Si a H 2a+1 → (SiR3)2A(Si a H 2a+1 ) + X-SiR3 (SiR3)2A(Si a H 2a+1 ) + X-Si b H 2b+1 → (SiR3)A(Si a H 2a+1 )(Si b H 2b+1 ) + X-SiR3 (SiR3)A(Si a H 2a+1 )(Si b H 2b+1 ) + X-Si c H 2c+1 → A(Si a H 2a+1 )(Si b H 2b+1 )(Si c H 2c+1 ) + X-SiR3; Alternatively, a one-pot reaction with a mixture of two or three halosilanes: A(SiR3)3 + x X-Si a H 2a+1 + y X-Si b H 2b+1 + from X-Si c H 2c+1 → A(Si a H 2a+1 ) x (Si b H 2b+1 ) y (Si c H 2c+1 ) z (SiR3) (3-x-y-z) + (x + y + z) X-SiR3, in X = Cl, Br, or I; a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c; m = 1 to 3; n = 1 to 2, p = 1 to 2, n + p = 2 to 3; x = 0 to 3, y = 0 to 3, z = 0 to 3, x + y + z = 1 to 3; A = elements selected from group V, namely As, P, Sb, and Bi; and R is selected from C1 to C. 10 Straight-chain, branched, or cyclic alkyl, alkenyl, or alkynyl groups.

2. The method as described in claim 1, wherein, Add a solvent selected from alkanes or aromatics or haloalkylsilanes or mixtures thereof, wherein the ratio of the solvent to A(SiR3)3 is 0-99 wt%.

3. The method as described in claim 1, wherein, The ratio of one or more halosilanes to A(SiR3)3 ranges from 1:99 to 99:

1.

4. The method of claim 1, wherein, X is Cl.

5. The method of claim 1, wherein, The halosilane is Cl-SiH3, Cl-Si2H5, or Cl-Si3H7.

6. The method of claim 1, wherein, R stands for methyl (Me).

7. The method of claim 2, further comprising: To separate the solvent and reaction products to isolate the compound containing a Group V element; and Purify the compound containing group V elements.

8. The method according to any one of claims 1 to 6, wherein, The purity of this compound containing group V elements is > 93%.

9. The method according to any one of claims 1 to 6, wherein the method is a batch process.

10. The method according to any one of claims 1 to 6, wherein, These reactions are maintained at temperatures ranging from -20°C to 150°C.

11. The method according to any one of claims 1 to 6, wherein, The group V element-containing compound is selected from the group consisting of P(SiH3)3, P(SiR3)(SiH3)2, P(SiR3)2(SiH3), P(SiR3)(Si2H5)2, P(SiR3)2(Si2H5), P(Si2H5)3, P(SiR3)(Si3H7)2, P(SiR3)2(Si3H7), P(Si3H7)3, As(SiH3)3, As(SiR3)(SiH3)2, As(SiR3)2(SiH3), As(SiR3)(Si2H5)2, As(SiR3)2(Si2H5), As(Si2H5)3, As(SiR3)(Si3H7)2, As(SiR3)2(Si3H7), As(Si3H7)3, Sb(SiH3)3, Sb(SiR3)(SiH3)2, Sb(SiR3)2(SiH3), Sb(SiR3)(Si2H5)2, Sb(SiR3)2(Si2H5), Sb(Si2H5)3, Sb(SIR3)(Si3H7)2, Sb(SiR3)2(Si3H7), Sb(Si3H7) 3， P(SiR3)(SiH3)(Si2H5), P(SiR3)(SiH3)(Si3H7), P(SiH3)2(Si2H5), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7), P(Si2H5)(Si3H7)2, As(SiR3)(SiH3)(Si2H5), As(SiR3)(SiH3)(Si3H7), As(SiH3)2(Si2H5), As(SiH3)2(Si3H7), As(SiH3)(Si2H5)2, As(SiH3)(Si2H5)(Si3H7), As(SiH3)(Si3H7)2, As(Si2H5)2(Si3H7), As(Si2H5)(Si3H7)2, Sb(SiR3)(SiH3)(Si2H5), Sb(SiR3)(SiH3)(Si3H7), Sb(SiH3)2(Si2H5), Sb(SiH3)2(Si3H7), Sb(SiH3)(Si2H5)2, Sb(SiH3)(Si2H5)(Si3H7), Sb(SiH3)(Si3H7)2, Sb(Si2H5)2(Si3H7), or Sb(Si2H5)(Si3H7)2, wherein R is selected from Me, Et, nPr, iPr, tBu, nBu, iBu or sBu.

12. The method according to any one of claims 1 to 6, wherein, When R is Me, the group 15 element-containing compound is selected from P(SiH₃)₃, P(TMS)(SiH₃)₂, P(TMS)₂(SiH₃), P(TMS)(Si₂H₅)₂, P(TMS)₂(Si₂H₅), P(Si₂H₅)₃, P(TMS)(Si₃H₇)₂, P(TMS)₂(Si₃H₇), P(Si₃H₇)₃, As(SiH₃)₃, As(TMS)(SiH₃)₂, As(TMS)₂(SiH₃), As(TMS)(Si₂H₅)₂, As(TMS)₂(Si₂H₅), As(Si₂H₅)₃, As(TMS)(Si₃H₇)₂, As(TMS)₂(Si₃H₇), As(Si₃H₇)₃, Sb(SiH₃)₃, Sb(TMS)(SiH₃)₂, Sb(TMS)₂(SiH₃), Sb(TMS)(Si₂H₅)₂, Sb(TMS)₂(Si₂H₅), Sb(Si₂H₅)₃, Sb(TMS)(Si₃H₇)₂, Sb(TMS)₂(Si₃H₇), Sb(Si₃H₇) 3， P(TMS)(SiH₃)(Si₂H₅), P(TMS)(SiH₃)(Si₃H₇), P(SiH₃)₂(Si₂H₅), P(SiH₃)₂(Si₃H₇), P(SiH₃)(Si₂H₅)₂, P(SiH₃)(Si₂H₅)(Si₃H₇), P(SiH₃)(Si₃H₇)₂, P(Si₂H₅)₂(Si₃H₇), P(Si₂H₅)(Si₃H₇)₂, As(TMS)(SiH₃)(Si₂H₅), As(TMS)(SiH₃)(Si₃H₇), As(SiH₃)₂(Si₂H₅), As(SiH₃)₂(Si₃H₇), As(SiH₃)(Si₂H₅)₂, As(SiH₃)(Si₂H₅)(Si₃H₇), As(SiH₃)(Si₃H₇)₂, As(Si₂H₅)₂(Si₃H₇), As(Si₂H₅)(Si₃H₇)₂, Sb(TMS)(SiH₃)(Si₂H₅), Sb(TMS)(SiH₃)(Si₃H₇), Sb(SiH₃)₂(Si₂H₅), Sb(SiH₃)₂(Si₃H₇), Sb(SiH₃)(Si₂H₅)₂, Sb(SiH₃)(Si₂H₅)(Si₃H₇), Sb(SiH₃)(Si₃H₇)₂, Sb(Si₂H₅)₂(Si₃H₇), or Sb(Si₂H₅)(Si₃H₇)₂.

13. The method according to any one of claims 1 to 6, wherein, When A = When P is present, the compound containing a group V element is selected from the group consisting of: P(SiH3)3, P(TMS)(SiH3)2, P(TMS)2(SiH3), P(TMS)(Si2H5)2, P(TMS)2(Si2H5), P(Si2H5)3, P(TMS)(Si3H7)2, P(TMS)2(Si3H7), P(Si3H7)3, P(TMS)(SiH3)(Si2H5), P(TMS)(SiH3)(Si3H7), P(SiH3)2(Si2H5), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7) and P(Si2H5)(Si3H7)2.

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