Novel inorganic silyl and polysilyl derivatives of group V elements and methods for their synthesis and use for deposition - Patents.com

Abstract

Disclosed are Group V element-containing precursors, methods for their synthesis, and methods for their use in film deposition. The precursor is (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 ) (wherein a=1-6; b=1-6; c=1-6; a≠b≠c; m=1-3; n=1-2, p=1-2, n+p=2-3; A=As, P, Sb, Bi; R is C1-C 10 (A is selected from linear, branched, or cyclic alkyl, alkenyl, alkynyl groups of A). Synthesis methods include one-step, two-step, or three-step reaction between halo(poly)silanes and tris(trialkylsilyl) derivatives of A, or one-pot mixture reaction of two or three halo(poly)silanes with a mixture of tris(trialkylsilyl) derivatives of A. Deposition methods include CVD, PECVD, ALD, PEALD, flowable CVD, HW-CVD, epitaxy, etc.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of 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.

[0002] The present invention relates to a Group V element-containing precursor, in particular a Group V element-containing precursor having the general formula: (SiR3) 3-m A(Si a H 2a+1 ) m or (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 ) (In these formulas, a=1-6; b=1-6; c=1-6; a≠b≠c; m=1 to 3; n=1 to 2, p=1 to 2, and n+p=2 to 3; A=As, P, Sb, Bi; R is C1~C 10 linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups, Methods for its synthesis and its use in semiconductor film deposition include one-step, two-step, or three-step reaction between a halo(poly)silane and a tris(trialkylsilyl) derivative of A, or a one-pot mixture reaction of a mixture of two or three halo(poly)silanes with a tris(trialkylsilyl) derivative of A; and methods for depositing films containing Si and group V elements, including CVD, PECVD, ALD, PEALD, flowable CVD, HW-CVD, epitaxy, etc. [Background technology]

[0003] Thin films containing Group V elements are used in a variety of applications including p-doped Si or SiGe semiconductor channel and contact layers in solid-state transistors, non-volatile phase change memories (PCMs), solar cells, III-V compounds, and optical storage materials, etc. III-V compound semiconductors can be used in many different applications including transistors, optoelectronics, and other applications, such as, for example, bipolar transistors, field effect transistors, lasers, IR detectors, LEDs, wide band gap semiconductors, quantum well or quantum dot structures, solar cells, and monolithic microwave integrated circuits.

[0004] Several III-V semiconductors exhibit attractive characteristics for use in solid-state electronic devices, such as high thermal stability, high electron mobility, and low band gaps. However, III-V semiconductors are more difficult to synthesize than the widely used group IV semiconductors, and the lack of suitable routes to III-V compounds has hindered their acceptance as alternatives to group IV compounds.

[0005] Some Group V element-containing compounds (or Group V compounds) have been prepared using silyl and polysilyl ligands, namely P(SiH3)3, P(Si2H5)3, and As(SiH3), etc. The use of such compounds for thin film deposition processes has been disclosed for P(SiH3)3 for epitaxial applications as a phosphorus dopant by forming interconnected III-V-(IV)3 "building blocks" (ref), resulting in highly stable crystal structures with, on average, diamond-like symmetry.

[0006] Relevant prior art includes the following:

[0007] Tice et al. (Dalton Trans., 2010, 39(19), 4551-4558) disclose that P(SiH3)3 can be synthesized by the reaction P(SnMe3)3 + 3SiH3Br → (SiH3)3P + 3Me3SnBr.

[0008] Amberger et al. (Angew. Chem. Int. Ed., 1962, 1, 52) disclose that (SiH3)3P can be synthesized in about 55% yield by 3KPH2 + 3SiH3Br → P(SiH3)3 + 2PH3 + 3KBr.

[0009] Amberger et al. (Angew. Chem., 1962, 74, 293) disclose that under mild conditions, (SiH3)3As can be synthesized and isolated in about 50% yield by the reaction 3KAsH2 + 3SiH3Br → As(SiH3)3 + 2AsH3 + 3KBr.

[0010] Amberger et al. (Zeitschrift für Naturforschung 1963,18b 157) also disclose the preparation and properties of trisilylstibine by the reaction of Li3Sb+SiH3Br in ether at low temperature, followed by isolation of the lights to give Sb(SiH3)3 in 77%.

[0011] Drake et al. (J. Chem. Soc., 1969, 662-665) disclose the synthesis of P(Si2)3 by reacting an appropriate amount of diborane with Si2-PH2: 3SiH3SiH2PH2→(promoted by B2H6)P(Si2H5)3+2PH3.

[0012] Drake at al. (Inorg. Chem., 1967, 6(11). 1984-1986; Chem. Ind., 1962, 1470) disclose the synthesis and purification of monosilylphosphines such as SiH3SiH2-PH2 by inductive decomposition of a mixture of monosilane and phosphine with the silent discharge of an ozone generator, followed by trap-to-trap distillation.

[0013] Drake at al. (J. Chem. Soc. A., 1968, 2709) discloses the disproportionation of GeH3PH2 to form (GeH3)3P.

[0014] Drake et al. (J. Chem. Soc. A, 1971, 13, 2246) disclose that the reaction of P(SiH3)3 with LiAlH4 gives, for example, LiAlH[P(SiH3)2]3+Si2H5Br→Si2H5-P(SiH3)2 as one of the products.

[0015] Drake et al. (Inorg. Nucl. Chem. Letters, 1968, Vol. 4, pp 361-363) disclose that monobromogermane reacts with trisilylphosphine to "exchange" and form trigermylphosphine. Monobromosilane reacts with KMH2 (M = P, As, Sb) to give trisilyl rather than monosilyl derivatives, and monoiodosilane reacts with disilylamine to give trisilyl species.

[0016] Cradock et al. (J. Chem. Soc. A., 1967, 1229) disclose the exchange reaction of GeH3Br-(SiH3)3P to form (GeH3)3P.

[0017] Wingeleth et al. (Phosphorus and Sulfur and the related Elements, 1988, 39, 123-9) disclose the formation of P(SiH3)3, P(Si2H5)3, P(SiH3)2(Si2H5), and P(GeH3)3 by the redistribution reaction of monosilylphosphines or monogermylphosphines including SiH3PH2, Si2H5PH2, SiH3PH2 / Si2H5PH2, and GeH3PH2 promoted by BX3, B2H6, and B5H9.

[0018] Beagley et al., (Chem. Commun., 1967, 12, 601-602) disclose gas phase pyramidal structures of P(SiH3)3 and As(SiH3)3.

[0019] Yang et al. (Chem. Mater. 2014, 26, 14, 4092-4101) disclose that a low-temperature reaction between P(SiH3)3 and an Al atomic beam leads to the formation of an Al-P(SiH3)3 intermediate containing an Al-PSi3 core, which was recently confirmed to be capable of depositing and matching on the Si(100) lattice, thus providing a practical route for the growth of III-V materials on Group IV semiconductors.

[0020] Watkins et al. (J. Am. Chem. Soc. 2011, 133, 40, 16212-16218) disclose the preparation, characterization, and theoretical simulation of tetragonal distorted Al-PSi3 cores grown on Si(100).

[0021] A similar application has been disclosed in Chizmeshya et al. (ECS Transactions, 2012, 50(9), 623-634) for the formation of intermediates with Al-PSi3 cores using molecular beam epitaxy (MBE) techniques at <600°C, followed by incorporation into diamond-shaped group IV materials. In a similar manner, not only can Al-AsSi3 be deposited using As(SiH3)3 precursor, but also P / As, As / N, and P / N hybrids can be deposited by forming the corresponding intermediates using a mixture of As(SiH3)3, P(SiH3)3, and N(SiH3)3 and reacting with Al. This work demonstrated that Al-PSi3 can be deposited by introducing a precursor mixture of P(SiH3)3 and P(GeH3)3. 3x Ge 3(1-x) This can be extended to deposits of

[0022] Sims et al. (Chem. Mater. 2015, 27, 8, 3030-3039) reported Al(BH4) films formed by a low-PCVD process using precursors P(SiH3)3 and Al(BH4)3 and grown on Si-based solids. 1-x B x Hybrids of Group III materials such as PSi3 (x=0.04-0.06) have been disclosed.

[0023] Kouvetakis et al. (Chem. Mater. 2012, 24, 16, 3219-3230) disclose the use of M(SiH3)3 (M=P, As) and Al to synthesize (III-V)-(IV) alloys on Si substrates using gas source MBE. Addition of N(SiH3)3 to the reaction mixture under appropriate conditions results in the synthesis of novel hybrid materials Al(As 1-x N x )Si3 and Al(P 1-x N x ) y S 5-2y was obtained.

[0024] WO 2019066825 / US 20200168462 to Romero et al. discloses the decomposition of Group V (including N, P, As, Sb, and Bi) and / or Group VI (including S, Se, and Te) materials using the corresponding hydride and / or silylated species (including silylated phosphines, arsines, stibines, bismuth, etc.).

[0025] Todd et al., U.S. Pat. No. 7,029,995, discloses a method for forming epitaxial films in which phosphorus, arsenic, and antimony are provided in the form of precursors such as phosphine, trisilylphosphine, arsine, trisilylarsine, stibine, and silylstibine.

[0026] Weeks et al., US Pat. No. 9,099,423, discloses doped semiconductor films and processes in which the dopant comprises phosphorus.

[0027] Todd, in U.S. Pat. No. 6,716,751, describes (HSi) 3-x MR x Silicon alloys and doped silicon films formed by CVD and ion implantation processes using Si-containing precursors including (HSi)N, (HSi)N, and (HSi)N, where R is H or D, x=0, 1, or 2, and M is selected from the group consisting of B, P, As, and Sb, are disclosed.

[0028] Dickson, U.S. Pat. No. 4,910,153, discloses a compound of formula (MX3): n M'X 4-n Disclosed is a deposition precursor having the formula: where M and M' are different Group 4A atoms, at least one of M and M' is silicon, X is hydrogen, halogen, or mixtures thereof, and n = 1-4 (endpoints included). The dopant has the formula (SiX3) m LX 3-m where L is a Group 5A atom selected from the group of P, As, Sb, and Bi; X is hydrogen, halogen, or mixtures thereof; and m is an integer from 1 to 3 (inclusive).

[0029] Formula A(SiH3) 3-x (H or D) x The use of compounds having the formula: is described, for example, in WO2002065508, especially when used in combination with a Si source that is a polysilane such as disilane or trisilane. This chemistry choice allows films to be deposited at lower temperatures than the traditional SiH4 / PH3 / AsH3 chemistry used in such processes, and therefore allows films to be deposited with dopant concentrations higher than the solubility value of the dopant in silicon. Summary of the Invention [Means for solving the problem]

[0030] A method for synthesizing a Group V element-containing compound is disclosed, the method comprising: A(SiR3)3, X-Si a H 2a+1 ,X-Si b H 2b+1 , and X-Si c H 2c+1 with one, two or three halo(poly)silanes selected from the group consisting of: The following graded overall reaction: a).One-step reaction: A(SiR3)3+mX-Si a H 2a+1 →(SiR3) 3-m A(Si a H 2a+1 ) m +mX-SiR3, b). Two-step reaction: A(SiR3)3+nX-Si a H 2a+1 →(SiR3) 3-n A(Si a H 2a+1 ) n +nX-SiR3 (SiR3) 3-n A(Si a H 2a+1 ) n+pX-(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 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 b H 2b+1 →A(Si a H 2a+1 )(Si b H 2b+1 )(Si c H 2c+1 )+X-SiR3; Due to Or a one-pot reaction using a mixture of two or three halo(poly)silanes: A(SiR3)3+xX-Si a H 2a+1 +yX-Si b H 2b+1 +zX-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 By dehalosilylating A(SiR3)3, a group V element-containing compound: (SiR3) 3-m A(Si a H 2a+1 ) m or (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 ) forming In these formulas: X=Cl, Br, or I; a=1-6; b=1-6; c=1-6; a≠b≠c; m=1 to 3; n=1 to 2, p=1 to 2, and n+p=2 to 3; x=0-3, y=0-3, z=0-3, and x+y+z=1-3; A=a V group element selected from As, P, Sb, and Bi; R is C1~C 10 The alkyl, alkenyl and alkynyl groups are selected from the group consisting of linear, branched and cyclic alkyl, alkenyl and alkynyl groups.

[0031] The disclosed methods may include one or more of the following aspects: Solvent is added the solvent is selected from an alkane or aromatic solvent, a haloalkylsilane, or a mixture thereof; The ratio of solvent to A(SiR3)3 is 0-99% by weight; · the alkane or aromatic solvent is selected from pentane, hexane, heptane, benzene, toluene, xylene, chlorotrimethylsilane, or mixtures thereof; · The ratio of halo(poly)silane to A(SiR3)3 ranges from 1:99 to 99:1; · The ratio of halo(poly)silane to A(SiR3)3 ranges from 1:20 to 20:1; · The ratio of halo(poly)silane to A(SiR3)3 is in the range of 1:5 to 5:1; X is Cl; · the halo(poly)silane is a chloro(poly)silane; Chloro(poly)silane is Cl-Si a H 2a+1 , Cl-Si b H 2b+1 , and / or Cl-Si a H 2a+1 wherein a=1 to 6; b=1 to 6; c=1 to 6; a≠b≠c; The chloro(poly)silane is Cl-SiH3, Cl-Si2H5, or Cl-Si3H7; R is a methyl group (Me); separating the solvent and the reaction products to isolate the Group V element-containing compound; and Purifying Group V element-containing compounds; Further includes; · Purity of group V-containing compounds is >90%; · Purity of group V-containing compounds is >95%; · Purity of group V-containing compounds is >98%; · The method is a batch process; · The reaction is maintained at a temperature ranging from -20°C to 150°C; · The reaction is maintained at a temperature ranging from room temperature to 100°C; The Group V-containing compound contains a trisilyl group; The trisilyl group is -SiH(SiH3)2(i-trisilyl); The trisilyl group is -SiH2-SiH2-SiH3 (n-trisilyl); Compounds containing group V elements are 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(Si R3)2(Si2H5), As(Si2H5)3, As(SiR3)(Si3H7)2, As(SiR3)2(Si3H7), As(Si3H7)3, Sb(SiH3)3, Sb(SiR3)(SiH3)2, Sb(Si R3)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; R is selected from Me, Et, nPr, iPr, tBu, nBu, iBu, or sBu; When R=Me, the group V-containing compounds are 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, selected from 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; · Compounds containing group V elements include P(SiH3)3, P(TMS)(SiH3)2, P(TMS)2(SiH3), P(TMS)(Si2H5)2, P(TMS)2(Si2H 5), P(Si2H5)3, P(TMS)(Si3H7)2, P(TMS)2(Si3H7), P(Si3H7)3, P(TMS)(SiH3)(Si2H5), P(T MS)(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; When n=2-3, the group V element-containing compound is 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 C1-C10). 10 linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups, with the exception of P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) when A=P; When n=3, the V-group element-containing compound is A(Si a H 2a+1 )3 (wherein a=1 to 6, A is a group V element selected from P, As, Sb, or Bi, and R is C1 to C 10 linear, branched, or cyclic alkyl, alkenyl, or alkynyl group, where a>1 when A=As; when A=P, P(Si2H5)3 is excluded; when A=Sb, Sb(SiH3)3 is excluded.

[0032] Also disclosed is a Group V element-containing compound, the Group V element-containing compound having the formula: (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 ) (In these formulas, a=1-6; b=1-6; c=1-6; a≠b≠c; m=1 to 3; n=1 to 2, p=1 to 2, and n+p=2 to 3; A=a group V element selected from As, P, Sb, and Bi; R is C1~C 10 (selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups) where A=As, As(SiH3)3 is excluded; where A=P, P(SiH3)3, P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) are excluded; where A=Sb, Sb(SiH3)3 is excluded. The disclosed compounds may include one or more of the following aspects: · Purity of group V-containing compounds is >93%; · Purity of group V-containing compounds is >95%; The purity of the Group V-containing compound is >98%.

[0033] Also disclosed is a method for forming a film containing Si and a group V element on a substrate, the method comprising: exposing the substrate to a vapor of a film-forming composition comprising a precursor containing Si and a Group V element; and depositing at least a portion of the precursor containing Si and a group V element on a substrate to form a film containing Si and a group V element on the substrate by a vapor deposition method; Including, The precursor containing Si and a group V element is represented by the general formula (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 ) (In these formulas, A is a group V element selected from P, As, Sb, or Bi; a=1-6; b=1-6; c=1-6; a≠b≠c; m=1 to 3; n=1 to 2, p=1 to 2, and n+p=2 to 3; R is C1~C 10 (selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups) where A=As, As(SiH3)3 is excluded; where A=P, P(SiH3)3, P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) are excluded; where A=Sb, Sb(SiH3)3 is excluded. The disclosed method may include one or more of the following aspects: Precursors containing group V elements are 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(Si R3)2(Si2H5), As(Si2H5)3, As(SiR3)(Si3H7)2, As(SiR3)2(Si3H7), As(Si3H7)3, Sb(SiH3)3, Sb(SiR3)(SiH3)2, Sb(Si R3)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; R is selected from Me, Et, nPr, iPr, tBu, nBu, iBu, or sBu; Precursors containing Si and group V elements are 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(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)( 3H7), 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; the precursor containing Si and a group V element is selected from the group consisting of 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; The deposition method includes a CVD process, an ALD process, an epitaxy process, or a combination thereof; The film-forming composition is activated by heating the substrate to a temperature in the range of 200°C to 1000°C, by activating a precursor containing Si and a group V element with a plasma, or a combination thereof; · further comprising exposing the substrate to a co-reactant; · The co-reactant is activated in the plasma; · The co-reactant is not activated in the plasma; the co-reactant is an oxygen-containing gas selected from O2, O3, H2O, H2O2, NO, N2O, NO2, O radicals, alcohols, silanols, aminoalcohols, carboxylic acids, paraformaldehyde, or combinations thereof; · The co-reactant is O3; the co-reactant is a nitrogen-containing gas selected from NH3, N2, H2, N2 / H2, H2 and NH3, N2 and NH3, NH3 and N2H4, NO, N2O, an amine, a trisilylamine, a silazane, or a combination thereof; · The co-reactant is H2; · The co-reactant is N2; the co-reactant is at least one secondary precursor selected from silane and polysilane, alkylsilane, halosilane (MCS, DCS, TCS, SiCl4), polyhalopolysilane, germane, chlorogermane, digermane, polygermane, halogermane, phosphine, borane, or halide-containing gas; The co-reactant is a diluent gas selected from Ar, He, N2, H2, or combinations thereof; The film containing Si and a group V element is a P-doped silicon-containing film; further comprising annealing the layer containing Si and a group V element by thermal annealing, furnace annealing, rapid thermal annealing, UV or electron beam curing, and / or plasma gas exposure; · The base material is a powder; The powder includes one or more of NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials.

[0034] In addition, the following formula: (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 ) (In these formulas, A is a group V element selected from P, As, Sb, or Bi; a=1-6; b=1-6; c=1-6; a≠b≠c; m=1 to 3; n=1 to 2, p=1 to 2, and n+p=2 to 3; R is C1~C 10 (selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups) Also disclosed is a film-forming composition for depositing a film comprising a precursor containing Si and a group V element having the formula: where, when A = As, As(SiH3)3 is excluded; when A = P, P(SiH3)3, P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) are excluded; and when A = Sb, Sb(SiH3)3 is excluded. The disclosed film-forming composition may include one or more of the following aspects: Precursors containing group V elements are 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(Si R3)2(Si2H5), As(Si2H5)3, As(SiR3)(Si3H7)2, As(SiR3)2(Si3H7), As(Si3H7)3, Sb(SiH3)3, Sb(SiR3)(SiH3)2, Sb(Si R3)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; R is selected from Me, Et, nPr, iPr, tBu, nBu, iBu, or sBu; When R=Me, precursors containing Si and group V elements are 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(TM S)2(Si2H5), 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(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)( 3H7), 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; The purity of the compound containing Si and group V elements is >93%; The purity of the compound containing Si and group V elements is >95%; The purity of the compound containing Si and group V elements is >98%.

[0035] Also disclosed is a wet film-forming composition for spin-coating a film comprising the disclosed Si and Group V element-containing precursor from 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: The Si and group V element containing precursor from formula (I), (II) or (III) having the lowest volatility is selected to remain in the spin-cast film during the annealing step and to decompose in-situ; further comprising a co-reactant which is a polysilane or mixture of polysilanes having 5 or more silicon atoms; The polysilane is cyclopentasilane; The polysilane is cyclohexasilane; further comprising a solvent; The spin-cast films are amorphous or polycrystalline Si films; · Spin-cast films are amorphous and polycrystalline Si films; The spin-cast film is an amorphous Si film; The spin-cast film is a polycrystalline Si film.

[0036] A method for forming a Group V element-doped epitaxial Si film on a substrate is also disclosed, the method comprising: maintaining the substrate at a predetermined temperature near the deposition temperature; exposing the substrate to a mixture of vapors of a film-forming composition comprising a precursor containing Si and a group V element and vapors of a co-reactant polysilane; depositing at least a portion of a precursor containing Si and a group V element on a substrate, and forming a group V element-doped epitaxial Si film on the substrate by a CVD process; The precursor containing Si and a group V element is represented by the general formula (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 ) (In these formulas, A is a group V element selected from P, As, Sb, or Bi; a=1-6; b=1-6; c=1-6; a≠b≠c; m=1 to 3; n=1 to 2, p=1 to 2, and n+p=2 to 3; R is C1~C 10 (selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups) where A=As, As(SiH3)3 is excluded; where A=P, P(SiH3)3, P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) are excluded; where A=Sb, Sb(SiH3)3 is excluded. The disclosed method may include one or more of the following aspects: the mixture includes a diluent gas selected from Ar, He, N2, H2, or combinations thereof; The co-reactant polysilane is germane; The given temperature is in the range of 200℃~1000℃; Deposition temperature ranges from 200℃ to 1000℃; When A is P, the group V element-doped epitaxial Si film is a P-doped epitaxial Si film.

[0037] Notation and Nomenclature In the following detailed description and claims, certain abbreviations, symbols, and terms that are commonly known in the art are utilized. A definition is typically provided with the first instance of each abbreviation, such as Stainless Steel (SS). Certain abbreviations, symbols, and terms are used throughout the following description and claims, including the following:

[0038] In the following detailed description and claims, certain abbreviations, symbols and terms that are commonly known in the art are used.

[0039] As used herein, the indefinite articles "a" or "an" mean one or more.

[0040] As used herein, in the text or claims, "about" or "around" or "approximately" means ±10% of the stated value.

[0041] As used herein, "room temperature" in the text and claims means approximately 20°C to approximately 25°C.

[0042] As used herein, "atmospheric pressure" in the text or claims means about 1 atmosphere.

[0043] The term "substrate" refers to the material or materials on which the process is performed. The substrate may refer to a wafer having the material or materials on which the process is performed. The substrate may be any suitable wafer used in semiconductor, photovoltaic, flat panel, or LCD-TFT device manufacturing. The substrate may also have one or more layers of different materials from a previous manufacturing step already deposited thereon. For example, the wafer may include a silicon layer (e.g., crystalline, amorphous, porous, etc.), a silicon-containing layer (e.g., SiO2, SiN, SiON, SiCOH, etc.), a metal-containing layer (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.), or a combination thereof. Furthermore, the substrate may be planar or patterned. The substrate may be an organic patterned photoresist film. The substrate may include a layer of oxide (e.g., ZrO2-based materials, HfO2-based materials, TiO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc.) used as a dielectric material in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications, or a nitride-based film (e.g., TaN, TiN, NbN) used as an electrode. Those skilled in the art will recognize that the term "film" or "layer" as used herein refers to a thickness of any material disposed on or spread over a surface, which may be a trench or line. Throughout this specification and claims, the wafer and any associated layers thereon are referred to as the substrate.

[0044] The term "wafer" or "patterned wafer" refers to a wafer having a stack of films on a substrate, with at least a top film having topographical features formed in a step prior to deposition of the indium-containing film.

[0045] The term "aspect ratio" refers to the ratio of the height of a trench (or aperture) to the width of the trench (or diameter of the aperture).

[0046] It should be noted that the terms "film" and "layer" may be used interchangeably herein. It is understood that a film may correspond to or be associated with a layer, and a layer may refer to a film. Furthermore, one of ordinary skill in the art will appreciate that the terms "film" or "layer" as used herein refer to any material of some thickness disposed on or spread across a surface, which may range from a surface as large as an entire wafer to a surface as small as a trench or line.

[0047] It should be noted that, as used herein, the terms "aperture," "via," "hole," and "trench" may be used interchangeably to refer to an opening formed in a semiconductor structure.

[0048] As used herein, the abbreviation "NAND" refers to a "Negative AND" or "Not AND" gate, the abbreviation "2D" refers to a two-dimensional gate structure on a planar substrate, and the abbreviation "3D" refers to a three-dimensional or vertical gate structure in which the gate structures are stacked vertically.

[0049] It should be noted that, in this specification, the terms "deposition temperature" and "substrate temperature" may be used interchangeably. It is understood that substrate temperature may correspond to or be related to deposition temperature, and deposition temperature may refer to substrate temperature.

[0050] It should be noted that, in this specification, the terms "precursor" and "deposition compound" and "deposition gas" may be used interchangeably when the precursor is in a gaseous state at room temperature and ambient pressure. It is understood that a precursor may correspond to or be related to a deposition compound or deposition gas, and a deposition compound or deposition gas may refer to a precursor.

[0051] Standard abbreviations of elements from the Periodic Table of Elements are used herein. It should be understood that elements can be referred to by such abbreviations (e.g., Si means silicon, N means nitrogen, O means oxygen, C means carbon, H means hydrogen, and Hal means halogen, which are F, Cl, Br, and I).

[0052] Unique CAS Registry Numbers assigned by the Chemical Abstract Service (ie, "CAS") are provided to identify particular molecules disclosed.

[0053] As used herein, the term "hydrocarbon" refers to saturated or unsaturated functional groups containing only carbon and hydrogen atoms.

[0054] It should be noted that silicon-containing films such as SiN and SiO are listed throughout the specification and claims without indicating their appropriate stoichiometry. Silicon-containing films include pure silicon (Si) layers such as crystalline Si, polysilicon (p-Si or polycrystalline Si) or amorphous silicon; silicon nitride (Si k N l ) layer; silicon oxide (Si n O m ) layer; or a mixture thereof, where k, l, m, and n are in the range of 0.1 to 6 (inclusive). Preferably, the silicon nitride is a SiN layer, where k and I are in the range of 0.5 to 1.5, respectively. k N l More preferably, the silicon nitride is Si3N4. In the following description, SiN is Si k N l It may be used to represent a silicon-containing layer. Preferably, silicon oxide is a Si n O m More preferably, the silicon oxide is SiO2. In the following description, SiO means Si n O mis used to represent a silicon-containing layer. 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 the Black Diamond II or III materials by Applied Materials, Inc., having the formula SiOCH. The silicon-containing film is a Si-containing layer, where a, b, and c are in the range of 0.1 to 6. a O b N c The silicon-containing film may also include Group III, IV, V, and VI dopants, such as B, C, P, As, and / or Ge.

[0055] It should be noted that deposited films or layers such as silicon oxide or silicon nitride may be described throughout the specification and claims without indicating their appropriate stoichiometry (i.e., SiO, SiO2, Si3N4). Layers include pure (Si) layers, carbide (Si O C p ) layer, nitride (Si k N l ) layer, oxide (Si n O m ) layers, or mixtures thereof, where k, l, m, n, o, and p range from 1 to 6, inclusive. For example, silicon oxide is Si n O m where n is in the range of 0.5 to 1.5, and m is in the range of 1.5 to 3.5. More preferably, the silicon oxide layer is SiO or SiO2. The silicon oxide layer may be a silicon oxide-based dielectric material, such as an organic-based or silicon oxide-based low-k dielectric material, such as Black Diamond II or III material by Applied Materials, Inc. Alternatively, the silicon-containing layer referred to may be pure silicon. The silicon-containing layer may also contain dopants, such as B, C, P, As and / or Ge.

[0056] As used herein, the abbreviation "Me" refers to a methyl group; the abbreviation "Et" refers to an ethyl group; the abbreviation "Pr" refers to any propyl group (i.e., n-propyl or isopropyl); the abbreviation "iPr" refers to an isopropyl group; the abbreviation "Bu" refers to any butyl group (n-butyl, isobutyl, tert-butyl, sec-butyl); the abbreviation "tBu" refers to a tert-butyl group; the abbreviation "sBu" refers to a sec-butyl group; the abbreviation "iBu" refers to an isobutyl group; the abbreviation "Ph" refers to a phenyl group; the abbreviation "Am" refers to any amyl group (isoamyl, sec-amyl, tert-amyl); 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 a trimethylsilyl-SiMe3 group.

[0057] Ranges may be expressed herein as from about one particular value and / or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and / or to the other particular value, along with all combinations within said ranges. Any ranges recited herein include their endpoints (i.e., x=1-4 or x is in the range of 1-4 includes x=1, x=4, and any number in between), regardless of whether the term "inclusive" is used.

[0058] Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with that embodiment may be included in at least one embodiment of the invention. The appearance of the phrase "in one embodiment" in various places in this specification does not necessarily all refer to that embodiment, nor do separate or alternative embodiments necessarily exclude other embodiments from one another. The same applies to the term "implementation."

[0059] As used in this application, the word "exemplary" is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present concepts in a concrete manner.

[0060] Additionally, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless otherwise specified or clear from the context, "X employs A or B" is intended to mean any of the reasonable inclusive permutations. That is, if X employs A, X employs B, or X employs both A and B, then "X employs A or B" is satisfied under any of the above cases. Additionally, the articles "a" and "an" as used in this application and the appended claims should generally be construed to mean "one or more" unless otherwise specified or clear from the context to the singular.

[0061] The foregoing and various other aspects, features, and advantages of the present invention, as well as the invention itself, can be more fully understood by reference to the following detailed description of the invention when considered in conjunction with the following drawings, which are provided for illustrative purposes only and are not intended to limit the invention, in which: [Brief description of the drawings]

[0062] [Figure 1] FIG. 1 is a GC chromatogram of the reaction mixture of P(TMS)3+7MCTS (monochlorotrisilane, i.e., Si3H7Cl) reacted in hexane at 68° C. for 24 hours (Example 2). [Diagram 2] FIG. 2 is a GC chromatogram of the reaction mixture of P(TMS)3+3MCS (monochlorosilane, i.e., SiH3Cl) reacted at 90° C. for 44 hours (Example 4). [Diagram 3] FIG. 3 is a GC chromatogram of the reaction mixture of As(TMS)3+6MCS reacted at 60° C. for 24 hours (Example 5). [Figure 4] FIG. 4 is a GC chromatogram of the reaction mixture of Sb(TMS)3+10MCS reacted at 60° C. for 24 hours (Example 8). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0063] Group V element-containing film-forming compositions comprising inorganic silyl and polysilyl-containing Group V element-containing precursors, methods for their synthesis, and methods for their use to deposit Group V element-containing films are disclosed.

[0064] The Group V element-containing precursors of the present disclosure have the general formula: (SiR3) 3-m A(Si a H 2a+1 ) m (I) (SiR3) 3-n-p A(Si a H 2a+1 ) n (Si b H 2b+1 ) p (II) A(Si a H 2a+1 )(Si b H 2b+1 )(Si c H 2c+1 ) (III) (In these formulas, A is a group V element selected from P, As, Sb, or Bi; a=1-6; b=1-6; c=1-6; a≠b≠c; m=1 to 3; n=1 to 2, p=1 to 2, and n+p=2 to 3; R is C1~C 10 (selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups) but when A = As, As(SiH3)3 is excluded; when A = P, P(SiH3)3, P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) are excluded; when A = Sb, Sb(SiH3)3 is excluded.

[0065] The group V element-containing precursors of the present disclosure contain a trisilyl group, which may be either -SiH(SiH3)2(i-trisilyl) or -SiH2-SiH2-SiH3(n-trisilyl).

[0066] Examples of precursors of the present disclosure 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(S iR3)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(Si3 H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si 3H7), P(Si2H5)(Si3H7)2, As(SiR3)(SiH3)(Si2H5), As(SiR3)(SiH3)(Si3H7), As(S iH3)2(Si2H5), As(SiH3)2(Si3H7), As(SiH3)(Si2H5)2, As(SiH3)(Si2H5)(Si3H7), Examples of such compounds include 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, where R is selected from Me, Et, nPr, iPr, tBu, nBu, iBu, or sBu.

[0067] Preferably, when R is a methyl group, -CH3, the group V element-containing precursor of the present disclosure is A(Si a H 2a+1 ) m (Si(CH3)3) 3-m or A(Si n H 2n+1 ) m (TMS) 3-m(wherein a=1-6; m=1-3; A is a group V element selected from P, As, Sb, or Bi), but a>1 when A=As; P(SiH3)2(TMS) is excluded when A=P; and Sb(SiH3)3 is excluded when A=Sb. When R=Me, examples of precursors of the present disclosure include 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(SiH 3)2(Si2H5), Sb(SiH3)2(Si3H7), Sb(SiH3)(Si2H5)2, Sb(SiH3)(Si2H5)(Si3H7), Sb(SiH3)(Si3H7)2, Sb(Si2H5)2(Si3H7), and Sb(Si2H5)(Si3H7)2.

[0068] Preferably, when n=2-3, the group V element-containing precursor of the present disclosure is 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 C1-C1H. 10 linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups, except that when A=P, P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS).

[0069] Preferably, when m=3, the group V element-containing precursor of the present disclosure is A(Si a H 2a+1 )3 (wherein a=1 to 6, A is a group V element selected from P, As, Sb, or Bi, and R is C1 to C10 where n>1 when A=As, P(Si2H5)3 is excluded when A=P, and Sb(SiH3)3 is excluded when A=Sb.

[0070] The group V element-containing precursors of the present disclosure are 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.

[0071] The disclosed synthetic method for synthesizing the Group V element-containing precursors of the present disclosure represented by formulas (I)-(III) comprises reacting a halosilyl or halopolysilyl compound (X-Si n H 2n+1 ) and A(SiR3)3, the tris(trialkylsilyl) derivative of A (A = As, P, Sb, or Bi): A(SiR3)3+mX-Si a H 2a+1 →A(Si a H 2a+1 ) m (SiR3) 3-m +mX-SiR3(IV) (Wherein, a=1 to 6; m=1 to 3, preferably m=3; A=As, P, Sb, Bi; X=Cl, Br, I; R is C1~C 10 and n is selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups.

[0072] The disclosed synthesis method comprises the steps of reacting A(SiR3)3 with halo(poly)silane (X-Si a H 2a+1 ), optionally with the addition of a solvent, in a ratio of halo(poly)silane to A(SiR3)3 ranging from 1-100 equivalents to 100-1 equivalents, preferably 1-20 equivalents to 20-1 equivalents, preferably the halo(poly)silane is a chloro(poly)silane. The solvent is preferably a chloro(poly)silane. a H 2a+1 ) is inert to both reactants and is selected from an alkane or aromatic solvent such as pentane, hexane, heptane, benzene, toluene, xylene, or a haloalkylsilane, or a mixture thereof, and represents 0-99% by weight of 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 obtain the desired precursor in the highest yield. The optimal ratio of halo(poly)silane to A(SiR3)3 can be optimized to reach the desired precursor in the highest yield. When a=1 or 2 in reaction (VI), monochlorosilane (MCS, ClSiH3) or monochlorodisilane (MCDS, ClSiH2SiH3) can be added neat or dissolved in a solvent using an airtight manifold, either by direct addition of the liquid or condensation of the neat vapor. The mixture of reactants is then stirred, typically for 1-168 hours, to form a reaction mixture. The product can then be separated from the reaction mixture by stripping of solvent and / or fractional distillation or other suitable means known in the art. The isolated product can then be purified, for example, by distillation, either batch or continuous, to reach a target product purity.

[0073] Here, the ratio of halo(poly)silane to A(SiR3)3 is in the range of 1:99 to 99:1, preferably 1:20 to 20:1, more preferably 1:10 to 10:1, and even more preferably 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 ranges from 1 to 168 hours, preferably 12 to 96 hours, and more preferably 24 to 48 hours, depending on the reaction conditions such as the reaction temperature.

[0074] Alternatively, the synthetic methods of the present disclosure can be carried out stepwise, where silyl groups of various sizes can be substituted sequentially, such as in a two- or three-step reaction.

[0075] The disclosed two-step reaction of a halosilyl or halopolysilyl compound with a tris(trialkylsilyl) derivative of A has the following general reaction: A(SiR3)3+nX-Si a H 2a+1 →(SiR3) 3-n A(Si a H 2a+1 ) n +nX-SiR3(V) (SiR3) 3-n A(Si a H 2a+1 ) n +pX-(Si b H 2b+1 ) →A(Si a H 2a+1 ) 3-n-p (Si b H 2b+1 ) p+ pX-SiR3(VI) (In these formulas, a=1-6 and b=1-6; n=1 to 2, p=1 to 2, and n+p=2 to 3; A=As, P, Sb, Bi; X=Cl, Br, I; R is C1~C 10 and wherein the alkyl, alkenyl, or alkynyl group is selected from the group consisting of linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups.

[0076] The disclosed three-step reaction of a halosilyl or halopolysilyl with a tris(trialkylsilyl) derivative of A has the following general reaction: A(SiR3)3+X-Si a H 2a+1 →(SiR3)2A(Si a H 2a+1 )+X-SiR3(VII) (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) (SiR3)A(Si a H 2a+1 )(Si b H 2b+1 )+X-Si b H 2b+1 →A(Si a H 2a+1 )(Si b H 2b+1 )(Si c H 2c+1 )+X-SiR3; (IX) (In these formulas, a=1-6, a=1-6, and c=1-6; A=As, P, Sb, Bi; X=Cl, Br, I; R is C1~C 10 and wherein the alkyl, alkenyl, or alkynyl group is selected from the group consisting of linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups.

[0077] Alternatively, the synthetic methods of the present disclosure can be carried out in a mixture or one-pot, where silyl groups of various sizes can be substituted in a mixture where all starting materials are mixed together.

[0078] The disclosed mixing reaction of a halosilyl or halopolysilyl with a tris(trialkylsilyl) derivative of A has the following general reaction: A(SiR3)3+xX-Si a H2a+1 +yX-Si b H 2b+1 +zX-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) (In the formula, a=1-6, b=1-6, and c=1-6; x=0-3, y=0-3, z=0-3, and x+y+z=1-3; A=As, P, Sb, Bi; X=Cl, Br, I; R is C1~C 10 and wherein the alkyl, alkenyl, or alkynyl group is selected from the group consisting of linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups.

[0079] In one embodiment, the disclosed synthetic method for synthesizing the disclosed Group V element-containing precursors represented by formulas (IV)-(X) includes the step of: a H 2a+1 , Cl-Si b H 2b+1 , and / or Cl-Si a H 2a+1 and a tris(trialkylsilyl) derivative of A (A = As, P, Sb, or Bi), A(SiR3)3 (R is C1-C 10 and a linear, branched, or cyclic alkyl, alkenyl, or alkynyl group selected from the group consisting of

[0080] The synthesis reactions of the present disclosure may be carried out in a batch mode. In this case, A(SiR3)3 may be added to a halo(poly)silane (e.g., a chloro(poly)silane) or vice versa. Addition of a halo(poly)silane to A(SiR3)3 may be preferred when only partial substitution of -SiR3 groups on A is desired.

[0081] The synthesis reaction of the present disclosure can be carried out in a continuous mode, where each reactant stream is continuously fed and reacted. A continuous mixing system may be used to aid in contacting the reactants. Although the reaction is not expected to produce solid by-products, a filtration step may be added after the synthesis to remove potential solid by-products as a precaution. Volatile by-products of the reaction may be continuously removed so that the reaction is driven to completion or multi-step conversion. This is an inherent advantage of the synthesis method of the present disclosure, where little or no solid by-products are produced. It is understood that the substitution of chloro(poly)silane reactants with bromo(poly)silanes does not deviate significantly. For reasons of availability, chlorosilanes are more convenient.

[0082] The synthetic method of the present disclosure has the following inherent advantages: Readily available starting materials: Existing synthetic methods use reactants such as KPH2 and P(SnMe3)3 that are either not commercially available or must be prepared fresh. In contrast, the disclosed synthetic method uses P(TMS)3, As(TMS)3, or Sb(TMS)3 as starting materials, which are commercially available in bulk at high purity. Chlorosilanes are also much more readily available than their Br counterparts. SiH3Cl (MCS) is commercially available. For example, Si2H5Cl (MCDS) and Si3H7Cl (MCTS) can be synthesized according to Cradock et al. (J. Chem. Soc. Dalton Trans., 1975, 1624-1628). The disclosed synthetic method can be a one-step synthesis when only one type of polysilyl group is introduced. Most existing synthetic methods are multi-step reactions, which require the preparation and subsequent isolation of mono- or disilylphosphines, such as SiH3PH2, Si2H5PH2, and LiAlH[P(SiH3)2]3, arsines, etc., in the first step. In contrast, the disclosed synthetic method is a one-step, single reactor process, which does not necessarily require isolation of by-products during the synthesis. The disclosed synthetic methods are mild reaction conditions. Due to the instability of the starting materials, most existing synthetic methods require reactions to be carried out at low temperatures with proper control of the rate of addition of reactants and / or the rate of melting of the mixture. In contrast, the disclosed synthetic methods are carried out at ambient to slightly elevated temperatures, such as temperatures ranging from room temperature to 100°C. The disclosed synthesis method has fewer side reactions and higher yields. The disclosed DHS route has fewer side reactions, resulting in relatively higher yields and facilitating the subsequent separation and purification processes. The disclosed synthetic methods result in little or no salt formation, which is known to promote the decomposition of similar molecules, such as N-based analogues with trisilylamine (TSA) backbone.

[0083] The disclosed Group V element-containing film-forming precursors synthesized by the disclosed synthesis methods can be used to vapor-deposit Si-containing films having Group V element dopants in silicon by CVD, PECVD, ALD, PEALD, flowable CVD, HW-CVD, epitaxy, and the like.

[0084] P and As compounds, especially their inorganic derivatives, e.g. As(Si x H y )3, P(Si x H y )3, where x and y can be the same or different for each silyl moiety, and y=2x+1, can be conveniently used as dopants in silicon. In some applications, it is highly desirable to dope beyond the solubility limit of the dopant in silicon, for example to reduce the contact resistance of semiconductor devices. Polysilanes and trisilanes can deposit silicon (e.g., amorphous or crystalline silicon) at a faster rate than silanes at temperatures below about 450° C. The Group V element-containing precursors of the present disclosure having polysilyl ligands instead of silyl ligands will also facilitate deposition and dopant incorporation at lower temperatures.

[0085] The Group V element-containing precursors of the present disclosure are delivered in high purity vessels, typically fabricated from stainless steel, carbon steel, or aluminum, that have been previously dried to less than 100 ppb residual HO and may optionally be passivated to limit the decomposition of the precursor therein over time. The passivation process typically involves exposing the high purity vessel to a silylating agent, which may be the precursor of interest itself or may be a silane or polysilane.

[0086] The Group V element-containing precursors of the present disclosure preferably have a purity of greater than 90% w / w (i.e., 93.0% w / w to 100.0% w / w), preferably greater than 95% w / w (i.e., 98.0% w / w to 100.0% w / w), 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), with metal impurities in the ppb range and O-containing impurities 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), more preferably less than 1% w / w (i.e., 0.0% w / w to 1.0% w / w). The Group V element-containing precursors of the present disclosure can be purified by recrystallization, sublimation, distillation, and / or gas-liquid passage through a suitable adsorbent material such as a molecular sieve.

[0087] The Group V element-containing precursors of the present disclosure can be provided in neat form or in a blend with a suitable solvent, such as ethylbenzene, xylene, mesitylene, decalin, decane, dodecane, or in a polysilane or haloalkylsilane. The precursors of the present disclosure can be present in a variety of concentrations in the solvent.

[0088] Vapor of the Group V element-containing precursor of the present disclosure can be delivered directly to the process chamber without a carrier gas, with the precursor having a vapor pressure typically >50 torr, preferably >300 torr, at a vessel temperature ranging from 0° C. to about 150° C.

[0089] For group V element-containing precursors of the present disclosure that have low vapor pressure, the vapor of the group V element-containing precursor of the present disclosure is delivered to the process chamber along with a carrier gas, either by bubbler, vapor aspirate, or direct liquid injection system. The carrier gas may include, but is not limited to, Ar, He, N2, H2, or combinations thereof. Dissolved oxygen present in the precursor may also be removed by bubbling with the carrier gas. The carrier gas and precursor are then introduced into the process chamber as a vapor. The process chamber is typically maintained at a pressure below atmospheric pressure, preferably in the range of 0.01 torr to 500 torr, more preferably in the range of 1 torr to 100 torr.

[0090] If necessary, the vessel containing the Group V element-containing precursor of the present disclosure may be heated or cooled to a temperature that allows the precursor to have sufficient and suitable vapor pressure. The vessel may be maintained at a temperature within the range of, for example, approximately 0° C. to approximately 200° C. Those skilled in the art will recognize that the temperature of the vessel may be adjusted as known in the art to control the amount of precursor that is vaporized.

[0091] The process chamber can be any enclosure chamber within the device in which the deposition method takes place, such as, but not limited to, a parallel plate reactor, cold wall reactor, hot wall reactor, single wafer reactor, multi-wafer reactor, or other type of deposition system under suitable conditions to cause reaction of the precursors and formation of the deposited film. One skilled in the art will appreciate that any of these process chambers may be used in either ALD or CVD deposition processes.

[0092] The process chamber contains one or more substrates on which the film is deposited. Substrates are generally defined as the material on which the process is performed. Substrates can be any suitable substrate used in semiconductor, photovoltaic, flat panel, or LCD-TFT device manufacturing. Examples of suitable substrates include wafers such as silicon, silica, glass, GaAs wafers, etc. The wafers can also have one or more layers of different materials from previous manufacturing steps deposited thereon. For example, the wafers can include a dielectric layer or a 3D NAND layer. Furthermore, the 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 oxide metal nitride layers (Ti, Ru, Ta, etc.), and combinations thereof. In addition, the wafers can include copper layers, precious metal layers (e.g., platinum, palladium, rhodium, gold). The wafers can include barrier layers such as manganese, manganese oxide, etc. Plastic layers can also be used. The layers may be planar or patterned. The deposition process of the present disclosure may deposit the layers directly onto the wafer or onto one or more layers on the wafer as the patterned layers are formed on the substrate. The patterned layers may be alternating layers of two specific layers, such as SiO and SiN, used in 3D NAND.

[0093] Although the end use of the substrate is not limited to the present invention, this technology may find particular advantage for substrate types such as silicon wafers, glass wafers and panels, beads, powders and nanopowders, monolithic porous media, printed circuit boards, plastic sheets, etc. Exemplary powder substrates include powders used in rechargeable battery technology. A non-limiting number of powder materials include NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials.

[0094] The temperature and pressure in the process chamber are maintained at conditions suitable for vapor deposition, such as ALD or CVD. In other words, after introducing the vaporized Group V element-containing precursor of the present disclosure into the chamber, the conditions in the chamber are such that at least a portion of the precursor deposits on the substrate to form a layer. For example, the pressure in the reactor or deposition pressure can be about 10 to 2000 psi, as required for each deposition parameter. -3 Torr to about 500 Torr, preferably about 10 -2 The pressure in the reactor may be maintained at from about 1000° C. to about 500 torr, more preferably from about 1 torr to about 100 torr. Similarly, the temperature in the reactor or deposition temperature may be maintained at from room temperature to about 1000° C., preferably from 200° C. to 800° C. One of ordinary skill in the art will recognize that "at least a portion of the precursor is deposited" means that some or all of the precursor reacts with the substrate and adheres to the substrate.

[0095] The temperature to achieve optimal film growth can be controlled by controlling the temperature of the substrate holder. The equipment used to heat the substrate is known in the art. The substrate is heated to a temperature sufficient to obtain the desired film having the desired physical state and composition at a sufficient growth rate. Non-limiting exemplary temperature ranges to which the substrate may be heated include approximately 200°C to approximately 800°C. If a plasma deposition process is utilized, the deposition temperature is preferably less than 500°C. Alternatively, if a thermal process is performed, the deposition temperature may range from 200°C to approximately 800°C.

[0096] Alternatively, the substrate may be heated to a temperature sufficient to obtain the desired deposited film having the desired physical state and composition at a sufficient growth rate. The temperature of the substrate may be maintained at a temperature in the range of about 200°C to 1000°C, preferably 200°C to 800°C, and more preferably 250°C to 600°C.

[0097] More specifically, in addition to the Group V element-containing precursors of the present disclosure, other precursors or co-reactants may be used, such as, but not limited to, H2, silanes, polysilanes (Si2-Si6, linear, branched, or cyclic for Si5 and Si6), alkylsilanes (such as monomethylsilane), halosilanes (Cl-SiH3, Cl2SiH2, I2-SiH2, Cl3SiH 、 SiCl4, polyhalopolysilanes (Si2Cl6, Si2HCl5, Cl-Si2H5, etc.), germane, chlorogermane, digermane, polygermane, halogermane, phosphine, boranes (B2H6, etc.), diborane, halide-containing gases (HCl, Cl2, HBr, etc.); N-containing gases (NH3, N2, N2 / H2, and NH3, N2 and NH3, NH3 and N2H4, NO, N2O, amines, trisilylamines, silazanes, etc., or combinations thereof); O-containing gases (O2, O3, H2O, H2O2, NO, N2O, NO2, O radicals, alcohols, silanols, aminoalcohols, carboxylic acids, paraformaldehyde, etc., and combinations thereof) may also be introduced into the process chamber.

[0098] Additionally, a diluent gas may be added to the process, which is selected from Ar, He, N2, H2, or combinations thereof.

[0099] Additionally, the co-reactant may be treated with plasma, which may utilize at least one of H2, N2, and O2, or inert gases (He, Ar, Kr, Xe), depending on the composition of the target film, when treated with plasma to decompose the precursor or reactant into its radical form. The plasma source may 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, the plasma may be generated with a power ranging from about 10 W to about 1000 W, preferably from about 50 W to about 500 W. The plasma may be generated and present within the reactor itself. Alternatively, the plasma may generally be present at a location remote from the reactor, such as in a remotely installed plasma system. Those skilled in the art will recognize suitable methods and apparatus for such plasma treatment.

[0100] For example, the co-reactant can be introduced into a direct plasma reactor that generates a plasma in the reaction chamber to generate plasma-treated reactants in the process chamber. Exemplary direct plasma reactors include the Titan™ PECVD system manufactured by Trion Technologies. The co-reactant can be introduced and maintained in the process chamber prior to plasma treatment. Alternatively, plasma treatment can be performed simultaneously with introduction of the precursor or reactant. The in-situ plasma is typically a 13.56 MHz RF inductively coupled plasma that is generated between a showerhead and a substrate holder. The substrate and showerhead can be electrodes that are powered depending on whether positive ion bombardment occurs. Typical applied power in the in-situ plasma generator is about 30 W to about 1000 W. Preferably, a power of about 30 W to about 600 W is used in the method of the present disclosure. More preferably, the power is in the range of about 100 W to about 500 W. Dissociation of the co-reactant using the in-situ plasma is typically less than that achieved using a remote plasma source at the same power input, and thus dissociation of the reactant is not as efficient as with remote plasma systems. Remote plasma systems can be useful for depositing films on substrates that are susceptible to plasma damage.

[0101] Alternatively, the plasma treated co-reactant can be generated outside the process chamber, for example in a remote plasma that treats the co-reactant before it enters the process chamber.

[0102] The deposition process may or may not be selective to a particular surface.

[0103] The deposition process may be thermally driven or may be enhanced by plasma activation, photoactivation, microwave activation, or other suitable means for activating the molecules and growth process.

[0104] The Group V element-containing film-forming composition of the present disclosure can be used to deposit a film using any deposition method known to those skilled in the art. Examples of suitable 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 a hot wire serves as the energy source for the deposition process), radical-incorporated CVD, and combinations thereof. Exemplary ALD methods include thermal ALD, plasma-enhanced ALD (PEALD), spatial ALD, hot-wire ALD (HWALD), radical-introduced ALD, and combinations thereof. The deposition method is preferably hot-wall or cold-wall thermal CVD, capable of depositing epitaxial or amorphous films containing Si and the dopant elements of the claimed compounds, and optionally Ge and / or other co-dopants.

[0105] In an ALD process, the ALD conditions in the chamber can cause the Group V element-containing film-forming composition of the present disclosure, adsorbed or chemisorbed on the substrate surface, to react and form a film on the substrate. In some embodiments, applicants believe that plasma-treating a co-reactant can provide the co-reactant with the energy necessary to react with the Group V element-containing film-forming composition of the present disclosure (PEALD). The co-reactant can be treated with plasma before or after introduction into the chamber.

[0106] The group V element-containing precursor and the co-reactant can be introduced into the reactor sequentially (ALD). The process chamber can be purged with an inert gas between each introduction of the group V element-containing precursor, the additional precursor, and the co-reactant. Another example is to continuously introduce the co-reactant and pulse the group V element-containing precursor while sequentially activating the co-reactant with a plasma (CWPEALD), provided that the group V element-containing precursor and the non-activated co-reactant do not substantially react at the temperature and pressure conditions of the chamber.

[0107] Each pulse of the group V element-containing precursor of the present disclosure may last for a time period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 second to about 80 seconds, alternatively from about 5 seconds to about 30 seconds. The co-reactant may also be pulsed into the reactor. In such an embodiment, each pulse may last for a time period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 second to about 30 seconds, alternatively from about 2 seconds to about 20 seconds. In another alternative, the vaporized group V element-containing precursor and the co-reactant may be sprayed simultaneously without mixing from different sectors of a showerhead under which a susceptor holding multiple wafers rotates (space ALD).

[0108] Depending on the specific process parameters, deposition may be carried out for a variety of times. In general, deposition may continue for the amount of time necessary to produce a film having the desired properties. Typical film thicknesses may vary from a few angstroms to hundreds of microns, typically between 2 and 100 nm, depending on the specific deposition process. The deposition process may also be carried out as many times as necessary to obtain the desired film.

[0109] The group V element-containing precursor and the co-reactant of the present disclosure can be introduced into the reactor either simultaneously (CVD), sequentially (ALD), or in different combinations thereof. Between the introduction of the group V element-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 element-containing precursor can be mixed together to form a co-reactant / compound mixture, which can then be introduced into the reactor in the form of a mixture (CVD, thermal CVD, or epitaxy). Another example is to introduce the co-reactant continuously and the group V element-containing precursor of the present disclosure in pulses (pulsed CVD).

[0110] The desired film thickness can be from a molecular monolayer to 10 μm, preferably in the range of 1 nm to 500 nm.

[0111] Depending on the co-reactant, the deposition process may include elements other than those present in the claimed precursors, such as Ge, Ga, C, B, Sn, Al, N, O, S, Se, Te, In, Zn, Cd, Hg, etc.

[0112] The films deposited using the deposition methods of the present disclosure may be films comprising p-doped Si and a group V element.

[0113] The films deposited using the deposition methods of the present disclosure may be Group V element doped silicon layers, such as P-doped silicon layers.

[0114] The Group V element-containing film-forming compositions of the present disclosure may be used for liquid phase film deposition of Si-containing films, including but not limited to spin coating, dip coating, or spray coating, in which a formulation containing the compounds of the present disclosure is coated onto a substrate and then annealed to obtain a thin film.

[0115] The Group V element-containing film-forming compositions of the present disclosure are particularly useful as doping components in formulations aimed at producing amorphous and polycrystalline Si films. Such formulations typically include large polysilanes or mixtures of polysilanes with 5 or more silicon atoms (cyclopentasilane, cyclohexasilane, etc.) and a solvent. After coating the substrate with the formulation, the film is treated to obtain a silicon film. For such spin-coating applications, the selected precursors should have the lowest volatility so that they remain in the spin-coated film during the annealing step and decompose in-situ. For such applications, precursors with at least 5 Si atoms are typically suitable.

[0116] The treatment typically involves heating (200-1000° C.) or / and light / UV exposure. In such formulations, the Group V element-containing compounds of the present disclosure can be added in proportions of 0.01%-50% (by weight) to obtain doped silicon films.

[0117] Formulations containing Group V element-containing precursors of the present disclosure can also be used to produce doped silicon oxide films by any of the wet coating methods previously described, by using oxidative curing after coating of the surface. 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, the curing involves a two-step process of a soft bake at temperatures ranging from room temperature to 250°C, and a hard bake at temperatures ranging from 250°C to 1000°C. The hard bake step can be performed with or without an oxidizing gas. For these wet coating applications, fully inorganic and low volatility precursors, preferably A(Si x H 2x+1 It is advantageous to use precursors selected from the group consisting of: x is 2 or more and A=As or P. EXAMPLES

[0118] The following non-limiting examples are provided to further illustrate embodiments of the present invention, however, the examples are not intended to be exhaustive and are not intended to limit the scope of the invention described herein.

[0119] Example 1. Synthesis of (TMS)2P(Si3H7) In a 20 mL vial, 3 g of Cl-Si3H7MCTS was added to 11 g of a 10 wt% solution of P(TMS)3 in hexane with magnetic stirring. The reaction mixture was stirred at room temperature under an inert atmosphere for 5 days, during which time all of the P(TMS)3 was converted to the majority of P(TMS)2(Si3H7) in 68% yield.

[0120] Example 2. Synthesis and characterization of P(Si3H7)3 25 g of P(TMS)3 was dissolved in 200 g of anhydrous hexane in a 500 mL flask under inert atmosphere, followed by slow addition of 75 g of monochlorotrisilane MCTS with magnetic stirring. The reaction mixture was refluxed at 68 °C for 24 h, during which time all of the P(TMS)3 was converted to P(Si3H7)3 in 93% yield. Figure 1 shows the GC chromatogram of the reaction mixture of P(TMS)3 + 7 MCTS reacted in hexane at 68 °C for 24 h.

[0121] Example 3. Synthesis of (TMS)P(SiH3)2 35 g of 10 wt% P(TMS) in hexane was placed in a 60 mL stainless steel vessel. 2.6 g of monochlorosilane MCS was cryotrapped inside the vessel. The reaction mixture was thawed and shaken at 150 rpm in a sealed vessel at 75 °C for 24 h. During that time, all of the P(TMS)3 was converted to the majority of P(TMS)(SiH3)2 in 59% yield.

[0122] Example 4. Synthesis of P(SiH3)3 5.6 g of P(TMS)3 was placed in a 60 mL stainless steel vessel. 6.9 g of monochlorosilane (MCS) was cryotrapped inside the vessel. The reaction mixture was thawed and shaken at 150 rpm in a sealed vessel at 90 °C for 48 h. During that time, all of the P(TMS)3 was converted to the majority of P(SiH3)3 with a yield of 85%.

[0123] 235 g of P(TMS)3 was placed in an airtight 600 mL Parr reactor. 183 g of monochlorosilane MCS was cryotrapped inside the vessel. The reaction mixture was thawed and vigorously stirred at 400 rpm at 90 °C for 44 h. During that time, all of the P(TMS)3 was converted to mostly P(SiH3)3 with a yield of 92%. Figure 2 shows the GC chromatogram of the reaction mixture of P(TMS)3 + 3MCS reacted at 90 °C for 44 h.

[0124] Example 5. Synthesis of As(Si3H7)3 A mixture of 2 g As(TMS)3 and 7.5 g MCTS in a 60 mL stainless steel vessel heated at 90 °C and shaken at 150 rpm for 48 h gives As(Si3H7)3 exclusively in 75% yield. Figure 3 shows the GC chromatogram of the reaction mixture As(TMS)3 + 6MCS (Example 5) reacted at 60 °C for 24 h.

[0125] Example 6. Synthesis of As(SiH3)(TMS)2 4.5 g of As(TMS)3 was placed in a 60 mL stainless steel vessel. 8.5 g of monochlorosilane (MCS) was cryotrapped inside the vessel. The reaction mixture was thawed and shaken at 150 rpm in a sealed vessel at 90 °C for 24 h. During this time, the majority of As(SiH3)(TMS)2 was obtained in 52% yield.

[0126] Example 7. Synthesis of Sb(Si3H7)(TMS)2 Sb(Si3H7)(TMS)2 can be synthesized in 72% yield by reacting 2 g of Sb(TMS)3 with 7 g of MCTS with vigorous magnetic stirring at room temperature for 1 day. It decomposes when heated at high temperatures (e.g., 50°C or 90°C).

[0127] Example 8. Synthesis of Sb(SiH3)(TMS)2 2.8 g of Sb(TMS)3 was placed in a 60 mL stainless steel vessel. 9 g of monochlorosilane MCS was cryotrapped inside the vessel. The reaction mixture was thawed and shaken at 150 rpm in a closed vessel at 60 °C for 24 h. During that time, the majority of Sb(SiH3)(TMS)2 was obtained in 23% yield. Figure 4 shows the GC chromatogram of the reaction mixture Sb(TMS)3 + 10MCS reacted at 60 °C for 24 h.

[0128] Example 9. Synthesis of P(Si2H5)3 5 g of a 10 wt% solution of P(TMS)3 in hexane was placed in a 60 mL stainless steel vessel. 2.2 g of monochlorodisilane MCDS was added to the vessel. The reaction mixture was shaken at 150 rpm in a closed vessel at 60 °C for 24 h. During that time, P(Si2H5)3 was formed in 22% yield.

[0129] Example 10. Isolation of P(SiH3)3 380 g of the synthesis mixture containing the product profile as 26% P(SiH3)3 in TMS-Cl solution was placed in a 500 mL round bottom flask in a glove box. A standard fractional distillation was then performed. After removal of volatiles at 55-70 °C, the main cut with vapor phase temperature in the range of 115-125 °C was collected at ambient pressure to obtain 75 g of P(SiH3)3 with a purity of 98%. This corresponds to an overall yield of 76%. It is expected that further distillation or distillation with higher separation efficiency can preferably achieve >99% for industrial applications.

[0130] Hypothetical Example 1: Synthesis of P(SiH3)2(Si3H7) 10 g of P(TMS)(SiH3)2 (e.g., synthesized in Example 3) was placed in a 60 mL stainless steel vessel at 30 wt% in TMS-Cl. 2.0 g of MCTS was added to the vessel. The reaction mixture was shaken at 150 rpm in a closed vessel at 75 °C for 24 h, during which P(SiH3)2(Si3H7) was formed as the main product.

[0131] Hypothetical Example 2: Synthesis of P(SiH3)(Si2H5)2 118 g of P(TMS)3 was placed in an airtight 600 mL Parr reactor. 31 g of monochlorosilane (MCS) was cryotrapped into the vessel. The reaction mixture was thawed and vigorously stirred at 75 °C and 400 rpm for 24 h. During that time, all of the P(TMS)3 was converted to a large extent to P(SiH3)(TMS)2.

[0132] 10 g of P(SiH3)(TMS)2, approximately 25 wt% in TMS-Cl, was placed in a 60 mL stainless steel vessel. 2.4 g of MCDS was added to the vessel. The reaction mixture was shaken at 150 rpm in a closed vessel at 60 °C for 40 h. During that time, P(SiH3)(Si2H5)2 was formed as the major product.

[0133] Hypothetical Example 3. CVD of P-doped Si layers using precursor P(Si3H7)3 An attempt is made to deposit a P-doped Si layer on a Si(100) substrate. Vapors of P(Si3H7)3 are introduced into a deposition reactor (heated to about 500 °C) at a flow rate of 10 sccm and a pressure of about 1-20 torr for 10-20 minutes. During that time, a polycrystalline P-doped silicon film with a thickness of 500-1500 Å is obtained. SEM images of the resulting P-doped silicon film can be acquired. An energy dispersive X-ray spectrometry (EDAX) detector can be used to perform elemental analysis. AFM, XRD, and ellipsometry measurements of the P-doped silicon film deposited on the Si(100) surface may be performed. Various other characterization techniques such as atomic absorption (AA), MS-GC, NMR, FT-IR, neutron activation analysis (NAA), energy dispersive analysis with X-rays (EDAX), Rutherford backscattering analysis (RBS), and X-ray analysis may be used to characterize the deposited film.

[0134] Hypothetical Example 4: Thermal CVD of high-quality P-doped Si layers on Si(100) wafers using the precursor P(SiH3)2(Si3H7) Si(100) substrates, pre-etched in dilute HF acid and properly conditioned (rinsed and dried), are loaded into the deposition chamber, followed by a H2 bake at 800-1000 °C with a flow rate of 50-120 slm. The substrate and chamber are then equilibrated at 400-600 °C with a back pressure of 20-50 torr. Pure H2 gas is then bubbled through the liquid precursor P(SiH3)2(Si3H7) and vapor of the P(SiH3)2(Si3H7) / H2 mixture is delivered to the reactor chamber at a flow rate of 50-150 sccm for 1-5 min. Highly crystalline P-doped epitaxial Si films of approximately 30-150 Å thickness are deposited on the Si(100) wafers. The absence of hydrogen residues can be confirmed by RBS.

[0135] Hypothetical Example 5: High-throughput thermal CVD of P-doped Si films on Si(100) wafers using precursor P(SiH3)(Si3H7)2 Si(100) substrates, pre-etched in dilute HF acid and appropriately conditioned (rinsed and dried), are loaded into the deposition chamber, followed by a H bake at 800-1000 °C with a flow rate of 50-120 slm. The substrate and chamber are then equilibrated at 550 °C with a back pressure of 50 torr. Pure H gas is then bubbled through the liquid precursor P(SiH3)2(Si3H7), which is equilibrated at about 75 °C, and then through room temperature trisilane into the mixing chamber at about 100 °C, followed by the vapor of the P(SiH3)(Si3H7)2 / Si3H8 / H2 mixture being introduced into the reaction chamber at a flow rate of about 100 sccm for 3 min. Highly crystalline P-doped epitaxial Si films of about 200 Å thickness are deposited on the Si(100) wafers.

[0136] Although the subject matter described herein may be described in the context of an example implementation of processing one or more computing application features / operations for a computing application having a user-interaction component, the subject matter is not limited to such particular implementation. Rather, the techniques described herein may be applied to any suitable type of user-interaction component execution management method, system, platform, and / or apparatus.

[0137] Those skilled in the art will recognize that many additional changes in the details, materials, steps, and arrangements of parts described and illustrated herein to explain the nature of the invention may be made within the principles and scope of the invention as set forth in the appended claims, and therefore, it is not intended that the invention be limited to the specific embodiments of the examples given above and / or the accompanying drawings.

[0138] Although embodiments of the present invention have been shown and described, modifications thereto may be made by those skilled in the art without departing from the spirit or teachings of the present invention. The embodiments described herein are merely exemplary and are not limiting. Many variations and modifications of the compositions and methods are possible and are within the scope of the present invention. Therefore, the scope of protection is not limited to the embodiments described herein, but is limited only by the scope of the following claims, which scope is intended to include all equivalents of the subject matter of the claims.

Claims

1. 1. A method for synthesizing a Group V element-containing compound, comprising the steps of: A(SiR ３ ) ３ X-Si ａ H ２ａ＋１ ,X-Si ｂ H ２ｂ＋１ , and X-Si ｃ H ２ｃ＋１ with one, two or three halo(poly)silanes selected from the group consisting of: The following graded overall reaction: a) One-step reaction: 2(3)2 ３ ) ) ３ +mX-3i ａ 8 ２ａ＋１ →(3iR ３ ) ) ３－ｍ 2(3) ａ 8 ２ａ＋１ ) ) ｍ +mX-3iｲ ３ 、 b) Two-step reaction: 2(3)2 ３ ) ) ３ +nX-3i ａ 8 ２ａ＋１ →(3iR ３ ) ) ３－ｎ 2(3) ａ 8 ２ａ＋１ ) ) ｎ +nX-3iｲ ３ (SiR ３ ) ３－ｎ A(Si ａ H ２ａ＋１ ) ｎ + pX-(Si ｂ H ２ｂ＋１ ) → (SiR ３ ) ３－ｎ－ｐ A(Si ａ H ２ａ＋１ ) ｎ (Si ｂ H ２ｂ＋１ ) ｐ＋ pX - SiR ３ or c) Three-step reaction: A(SiR ３ ) ３ +X-Si ａ H ２ａ＋１ →(SiR ３ ) ２ A(Si ａ H ２ａ＋１ )+X-SiR ３ (SiR ３ ) ２ A(Si ａ H ２ａ＋１ )+X-Si ｂ H ２ｂ＋１ →(SiR ３ )A(Si ａ H ２ａ＋１ )(Si ｂ H ２ｂ＋１ )+X-SiR ３ (SiR ３ )A(Si ａ H ２ａ＋１ )(Si ｂ H ２ｂ＋１ )+X-Si ｂ H ２ｂ＋１ →A(Si ａ H ２ａ＋１ )(Si ｂ H ２ｂ＋１ )(Si ｃ H ２ｃ＋１ )+X-SiR ３ ; Due to Or a one-pot reaction using a mixture of two or three halo(poly)silanes: 2(3)2 ３ ) ) ３ xX-3i ａ 8 ２ａ＋１ yX-3i ｂ 8 ２ｂ＋１ zX-3i ｃ 8 ２ｃ＋１ →A(3i ａ 8 ２ａ＋１ ) ) ｘ (3i) ｂ 8 ２ｂ＋１ ) ) ｙ (3i) ｃ 8 ２ｃ＋１ ) ) ｚ (3iｲ ３ ) ) （３－ｘ－ｙ－ｚ） +(x+yzz)X-3ii ３ Thus, A(SiR ３ ) ３ is dehalosilylated to obtain a Group V element-containing compound: (3iｲ ３ ) ) ３－ｍ 2(3) ａ 8 ２ａ＋１ ) ) ｍ 、 (SiR ３ ) 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 ) forming In these formulas: 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, and n+p=2 to 3; x=0 to 3, y=0 to 3, z=0 to 3, and x+y+z=1 to 3; A=a group V element selected from As, P, Sb, and Bi; R is C １ ~C １０ The method of claim 1, wherein the alkyl, alkenyl, or alkynyl group is selected from the group consisting of linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups.

2. A solvent selected from an alkane or aromatic or haloalkylsilane solvent, or a mixture thereof, is added, and A(SiR ３ ) ３ 2. The method of claim 1, wherein the ratio of said solvent to said base is 0 to 99% by weight.

3. Halo(poly)silanes vs. A (SiR ３ ) ３ The method of claim 1, wherein the ratio of is in the range of 1:99 to 99:

1.

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

5. The halo(poly)silane is Cl—SiH ３ , Cl-Si ２ H ５ , or Cl—Si ３ H ７ The method of claim 1, wherein

6. 2. The method of claim 1 , wherein R is a methyl group (Me).

7. separating the solvent and reaction product to isolate the Group V element-containing compound; and purifying said Group V element-containing compound; The method of any one of claims 1 to 6, further comprising:

8. The method of any one of claims 1 to 6, wherein the purity of the Group V element-containing compound is >93%.

9. The method according to any one of claims 1 to 6, which is a batchwise process.

10. 7. The process of any one of claims 1 to 6, wherein the reaction is maintained at a temperature in the range of -20°C to 150°C.

11. The V-group element-containing compound is P(SiH ３ ), P(SiR ３ )(SiH ３ ), P(SiR ３ )(SiH ２ ), P(SiR ３ )(SiH ２ ), P(SiR ３ )(Si ３ H ２ ), P(SiR ５ )(Si ２ H ３ ), P(Si ２ H ２ ), P(SiR ５ )(Si ２ H ５ ), P(SiR ３ )(Si ３ H ３ ), P(Si ７ H ２ ), P(SiR ３ )(Si ２ H ３ ), P(Si ７ H ３ ), As(SiH ７ ), As(SiR ３ )(SiH ３ ), As(SiR ３ )(SiH ３ ), As(SiR ３ )(Si ２ H ３ ), As(SiR ２ )(Si ３ H ３ ), As(Si ２ H ５ ), As(SiR ２ )(Si ３ H ２ ), As(Si ２ H ５ ), As(SiR ２ )(Si ５ H ３ ), As(SiR ３ )(Si ３ H ７ ), As(SiR ２ )(Si ３ H ２ ), As(Si ３ H ７ ), As(Si ３ H ７ ), Sb(SiH ３ ​ ３ ) ) ３ 、″b(″iｲ ３ )(3iｨ ３ ) ) ２ 、″b(″iｲ ３ ) ) ２ ｳiｨ ３ )、ｳbb｡i2 ３ )(3i ２ 8 ５ ) ) ２ 、″b(″iｲ ３ ) ) ２ (3i) ２ 8 ５ )、ｳbbii ２ 8 ５ ) ) ３ 、″b(″″ ３ )(3i ３ 8 ７ ) ) ２ 、″b(″iｲ ３ ) ) ２ (3i) ３ 8 ７ )、ｳbbii ３ 8 ７ ) ) ３、 Pｳi2 ３ )(3iｨ ３ )(3i ２ 8 ５ )、Pii2 ３ )(3iｨ ３ )(3i ３ 8 ７ )、P(Siｨ ３ ) ) ２ (3i) ２ 8 ５ )、P(Siｨ ３ ) ) ２ (3i) ３ 8 ７ )、P(Siｨ ３ )(3i ２ 8 ５ ) ) ２ 、.(ｳiｨ ３ )(3i ２ 8 ５ )(3i ３ 8 ７ )、P(Siｨ ３ )(3i ３ 8 ７ ) ) ２ 、.(3i ２ 8 ５ ) ) ２ (3i) ３ 8 ７ )、..(3i ２ 8 ５ )(3i ３ 8 ７ ) ) ２ 、Ashｳiｲ ３ )(3iｨ ３ )(3i ２ 8 ５ )、|s(3i2 ３ )(3iｨ ３ )(3i ３ 8 ７ )、|s(3iｨ ３ ) ) ２ (3i) ２ 8 ５ )、|s(3iｨ ３ ) ) ２ (3i) ３ 8 ７ )、|s(3iｨ ３ )(3i ２ 8 ５ ) ) ２ 、As(Siｨ ３ )(3i ２ 8 ５ )(3i ３ 8 ７ )、|s(3iｨ ３ )(3i ３ 8 ７ ) ) ２ 、As(ｳi ２ 8 ５ ) ) ２ (3i) ３ 8 ７ )、|s(3i ２ 8 ５ )(3i ３ 8 ７ ) ) ２ 、″b(″iｲ ３ )(3iｨ ３ )(3i ２ 8 ５ )、ｳbb｡i2 ３ )(3iｨ ３ )(3i ３ 8 ７ )、ｳbb(3iiｨ ３ ) ) ２ (3i) ２ 8 ５ )、ｳbb(3iiｨ ３ ) ) ２ (3i) ３ H ７ ), Sb(SiH ３ ) (Si ２ H ５ ) ２ , Sb(SiH ３ ) (Si ２ H ５ ) (Si ３ H ７ ), Sb(SiH ３ ) (Si ３ H ７ ) ２ , Sb(Si ２ H ５ ) ２ (Si ３ H ７ ), or Sb(Si ２ H ５ ) (Si ３ H ７ ) ２ 7. The method of any one of claims 1 to 6, wherein R is selected from Me, Et, nPr, iPr, tBu, nBu, iBu, or sBu.

12. When R is Me, the Group V element-containing compound is P(SiH ３ ) ３ , P(TMS)(SiH ３ ) ２ , P(TMS) ２ (SiH ３ ), P(TMS)(Si ２ H ５ ) ２ , P(TMS) ２ (Si ２ H ５ ), P(Si ２ H ５ ) ３ , P(TMS)(Si ３ H ７ ) ２ , P(TMS) ２ (Si ３ H ７ ), P(Si ３ H ７ ) ３ , As(SiH ３ ) ３ , As(TMS)(SiH ３ ) ２ , As(TMS) ２ (SiH ３ ), As(TMS)(Si ２ H ５ ) ２ , As(TMS) ２ (Si ２ H ５ ), As(Si ２ H ５ ) ３ , As(TMS)(Si ３ H ７ ) ２ , As(TMS) ２ (Si ３ H ７ ), As(Si ３ H ７ ) ３ , Sb(SiH ３ ) ３ , Sb(TMS)(SiH ３ ) ２ , Sb(TMS) ２ (SiH ３ ), Sb(TMS)(Si ２ H ５ ) ２ 、Sb (TMS) ２ (Si) ２ H ５ ),Sb (Si ２ H ５ ) ３ 、Sb(TMS)(Si ３ H ７ ) ２ 、Sb (TMS) ２ (Si) ３ H ７ ),Sb (Si ３ H ７ ) ３、 P(TMS)(SiH ３ )(Si ２ H ５ ), P(TA)(SiH ３ )(Si ３ H ７ ), P(SiH ３ ) ２ (Si) ２ H ５ ), P(SiH ３ ) ２ (Si) ３ H ７ ), P(SiH ３ )(Si ２ H ５ ) ２ ,P(SiH ３ )(Si ２ H ５ )(Si ３ H ７ ), P(SiH ３ )(Si ３ H ７ ) ２ ,P(Si ２ H ５ ) ２ (Si) ３ H ７ ), P(Si ２ H ５ )(Si ３ H ７ ) ２ 、As(TMS)(SiH ３ )(Si ２ H ５ ),As(TMS)(SiH ３ )(Si ３ H ７ ),As(SiH ３ ) ２ (Si ２ H ５ ),As(SiH ３ ) ２ (Si ３ H ７ ),As(SiH ３ )(Si ２ H ５ ) ２ 、As(SiH ３ )(Si ２ H ５ )(Si ３ H ７ ),As(SiH ３ )(Si ３ H ７ ) ２ 、As(Si ２ H ５ ) ２ (Si ３ H ７ ),As(Si ２ H ５ )(Si ３ H ７ ) ２ 、Sb(TMS)(SiH ３ )(Si ２ H ５ ),Sb(TMS)(SiH ３ )(Si ３ H ７ ),Sb (SiH ３ ) ２ (Si ２ H ５ ),Sb (SiH ３ ) ２ (Si ３ H ７ ),Sb (SiH ３ )(Si ２ H ５ ) ２ ,Sb (SiH) ３ )(Si ２ H ５ )(Si ３ H ７ ),Sb (SiH ３ )(Si ３ H ７ ) ２ 、Sb(Si ２ H ５ ) ２ (Si ３ H ７ ), or Sb(Si ２ H ５ ) (Si ３ H ７ ) ２ The method according to any one of claims 1 to 6, wherein the compound is selected from the group consisting of

13. When A = P, the Group V element-containing compound is P(SiH ３ ), P(TMS)(SiH ３ ), P(TMS) ３ ), P(TMS)(Si ２ H ２ ), P(TMS)(Si ３ H ２ ), P(Si ５ H ２ ), P(TMS)(Si ２ H ２ ), P(TMS)(Si ５ H ２ ), P(Si ５ H ３ ), P(TMS)(Si ３ H ７ ), P(TMS) ２ H ２ ), P(Si ３ H ７ ), P(TMS)(SiH ３ )(Si ７ H ３ ), P(TMS)(SiH ３ )(Si ２ H ５ ), P(SiH ３ )(Si ３ H ７ ), P(SiH ３ )(Si ２ H ２ ), P(SiH ５ )(Si ３ H ２ ), P(SiH ３ )(Si ７ H ３ )(Si ２ H ５ ), P(SiH ２ )(Si ３ H ２ )(Si ５ H ３ ), P(SiH ７ )(Si ３ H ３ ), P(Si ７ H ２ )(Si ２ H ５ ), and P(Si ２ H ３ )(Si ７ H ２ ), and P(Si ５ H ３ H ７ ) ２ The method according to any one of claims 1 to 6, wherein the compound is selected from the group consisting of

14. The following formula: (3iｲ ３ ) ) ３－ｍ 2(3) ａ 8 ２ａ＋１ ) ) ｍ 、 (SiR ３ ) 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 ) (In these formulas, 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, and n+p=2 to 3; A=a group V element selected from As, P, Sb, and Bi; R is C １ ~C １０ and selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups of the formula: However, when A=As, As(SiH ３ ) ３ is excluded; if A=P, P(SiH ３ ) ３ , P(SiH ３ ) ２ (Si ２ H ５ ), P(SiH ３ ) (Si ２ H ５ ) ２ , P(Si ２ H ５ ) ３ , and P(SiH ３ ) ２ (TMS) is excluded; if A=Sb, Sb(SiH ３ ) ３ Group V element-containing compounds are excluded.

15. 15. The Group V element-containing compound of claim 14, wherein the purity of the Group V element-containing compound is >98%.

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