Novel inorganic silyl and polysilyl derivatives of Group V elements, as well as methods for their synthesis and use for deposition.

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 on December 23, 2021, the entire content of which is incorporated herein by reference.

[0002] The present invention relates to group V element - containing precursors, particularly group V element - containing precursors having the following 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 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 = As, P, Sb, Bi; R is selected from linear, branched, or cyclic alkyl, alkenyl, alkynyl groups of C1 - C 10 ), Its synthesis method, and its use method in semiconductor film deposition, a one - step, two - step, or three - step reaction between a halo(poly)silane and a tris(trialkylsilyl) derivative of A, or a one - pot mixing reaction between a mixture of two or three halo(poly)silanes and a tris(trialkylsilyl) derivative of A; and deposition methods of films containing Si and group V elements, including CVD, PECVD, ALD, PEALD, fluidized 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 channels and contact layers in solid-state transistors, non-volatile phase-change memory (PCM), solar cells, Group III-V compounds, and optical memory materials. Group III-V compound semiconductors can be used in many different application areas, including transistors, optoelectronics, and other fields, such as bipolar transistors, field-effect transistors, lasers, IR detectors, LEDs, wide-bandgap semiconductors, quantum well or quantum dot structures, solar cells, and monolithic microwave integrated circuits.

[0004] Some III-V semiconductors exhibit attractive properties for use in solid-state electronic devices (e.g., high thermal stability, high electron mobility, and low band gap). However, III-V semiconductors are more difficult to synthesize than widely used IV semiconductors, and the lack of suitable routes to III-V compounds hinders their acceptance as substitutes for 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), among others. 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 a highly stable crystalline structure 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 is synthesized via 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 approximately 55% yield via 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 approximately 50% yield by the reaction 3KAsH2 + 3SiH3Br → As(SiH3)3 + 2AsH3 + 3KBr.

[0010] Amberger et al. (Zeitschrift fuer Naturforschung 1963, 18b 157) also disclose the preparation and characterization of trisilyl stibin by reacting Li3Sb + SiH3Br in ether at low temperature, followed by isolation of the light component to produce Sb(SiH3)3 at 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 et al. (Inorg. Chem., 1967, 6(11). 1984-1986; Chem. Ind., 1962, 1470) disclose the synthesis and purification of monosilylphosphines such as SiH3SiH2-PH2 by the induction decomposition of a mixture of monosilane and phosphine by silent discharge of an ozone generator, followed by trap-to-trap distillation.

[0013] Drake et al. (J. Chem. Soc. A., 1968, 2709) disclose the formation of (GeH3)3P by disproportionation of GeH3PH2.

[0014] Drake et al. (J.Chem.Soc.A,1971,13,2246) disclose that the reaction of P(SiH3)3 with LiAlH4 yields, 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 undergo "exchange," forming trigelmylphosphine. Monobromosilane reacts with KMH2 (M=P, As, Sb) to give trisilyl species rather than monosilyl derivatives, and monoiodosilane reacts with disilylamine to give trisilyl species.

[0016] Cradock et al. (J.Chem.Soc.A., 1967, 1229) disclose an exchange reaction that forms (GeH3)3P from GeH3Br-(SiH3)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, facilitated by BX3, B2H6, and B5H9.

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

[0019] Yang et al. (Chem.Mater.2014,26,14,4092-4101) disclosed that an Al-P(SiH3)3 intermediate containing an Al-PSi3 core is formed by a low-temperature reaction between P(SiH3)3 and an Al atomic beam. It has recently been confirmed that this can be deposited and matched on a Si(100) lattice, thus presenting a practical route for growing Group 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 strain Al-PSi3 cores grown on Si(100).

[0021] Chizmeshya et al. (ECS Transactions, 2012, 50(9), 623-634) disclose a similar application for forming an intermediate with an Al-PSi3 core using molecular beam epitaxy (MBE) technology at <600°C and then incorporating it into a diamond-shaped Group IV material. In a similar manner, not only can Al-AsSi3 be deposited using an As(SiH3)3 precursor, but P / As, As / N, and P / N hybrids can also be deposited by forming the corresponding intermediate using a mixture of As(SiH3)3, P(SiH3)3, and N(SiH3)3 and reacting it with Al. This study shows that by introducing a precursor mixture of P(SiH3)3 and P(GeH3)3, Al-PSi 3x Ge 3(1-x) It can be extended to the deposition of sediment.

[0022] Sims et al. (Chem.Mater.2015,27,8,3030-3039) describe a low-PCVD process using P(SiH3)3 and Al(BH4)3 precursors, and growing on a Si-based solid, Al 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 a (III-V)-(IV) alloy on a Si substrate using a gas source MBE. Adding N(SiH3)3 to the reaction mixture under appropriate conditions results in a novel hybrid material Al(As) 1-x N x )Si3 and Al(P 1-x N x ) y Si 5-2y This was obtained.

[0024] Romero et al.'s International Publication No. 2019066825 / U.S. Patent Application Publication No. 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 species (including silylated phosphines, arsine, stivin, and bismuth).

[0025] Todd et al.'s U.S. Patent No. 7029995 discloses a method for forming an epitaxial film in which phosphorus, arsenic, and antimony are supplied in the form of precursors such as phosphine, trisilylphosphine, arsine, trisilylarsine, stibine, and silylstibine.

[0026] Weeks et al.'s U.S. Patent No. 9,099,423 discloses a doped semiconductor film containing a phosphorus dopant and a process for treating it.

[0027] Todd’s U.S. Patent No. 6,716,751 states (H3Si) 3-x MR x Silicon alloys and doped silicon films formed by CVD and ion implantation processes using Si-containing precursors including (H3Si)3N and (H3Si)4N2 (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) are disclosed.

[0028] Dickson's U.S. Patent No. 4910153 contains the formula (MX3) n M'X 4-n A deposition precursor having the formula (SiX3) is disclosed, where M and M' are different group 4A atoms, at least one of M and M' is silicon, and X is hydrogen, a halogen, or a mixture thereof, with n=1 to 4 (including the endpoint). The dopant is of the formula (SiX3) m LX 3-m The formula has the following characteristics, where L is a group 5A atom selected from the group P, As, Sb, and Bi, X is hydrogen, a halogen, or a mixture thereof, and m is an integer from 1 to 3 (including the endpoint).

[0029] Formula A(SiH3) 3-x (H or D) x The use of compounds possessing this property is described, for example, in International Publication No. 2002065508, particularly when used in combination with a Si source that is a polysilane such as disilane or trisilane. This chemistry allows for film deposition at lower temperatures than conventional SiH4 / PH3 / AsH3 chemistry used in such processes, and thus enables the deposition of films with dopant concentrations higher than the solubility values ​​of the dopant in silicon. [Overview of the project] [Means for solving the problem]

[0030] A method for synthesizing compounds containing group V elements is disclosed, and this method is A(SiR3)3, X-Si a H 2a+1 ,X-Si b H 2b+1 , and X-Si c H 2c+1 Contacting one, two, or three types of halo(poly)silanes selected from the group consisting of the above, either in succession or as a mixture, and The following is the overall step-by-step response: 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; whereby, 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 is formed: (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 ) To form, These formulas include, 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 is a group V element selected from As, P, Sb, and Bi; R is C1~C 10 Selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups.

[0031] The disclosed methods may include one or more of the following embodiments: • A solvent is added. The solvent is selected from alkanes, aromatic solvents, haloalkylsilanes, or mixtures 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 is in the range of 1:99 to 99:1; • The ratio of halo(poly)silane to A(SiR3)3 is in the range of 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; • Halo(poly)silane is 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 In the equation, a = 1 to 6; b = 1 to 6; c = 1 to 6; and 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 reaction products to isolate compounds containing Group V elements; and Purification of compounds containing Group V elements; Further includes; • The purity of the compound containing group V elements is >90%; • The purity of the compound containing group V elements is >95%; • The purity of the compound containing Group V elements is >98%; The method is a batch process; • The reaction is maintained at a temperature in the range of -20°C to 150°C; • The reaction is maintained at a temperature ranging from room temperature to 100°C; • Compounds containing group V elements contain 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 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(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 Selected from 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; · If R=Me, then the group V element-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 Selected from the group consisting of 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 compounds are 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~C 10 The group is selected from the group consisting of linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups, but if A=P, then P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) are excluded; • If n=3, the compound containing group V elements is A(Si a H 2a+1 )3(In the formula, a = 1 to 6, A is a group V element selected from P, As, Sb, or Bi, and R is C1 to C 10 (Selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups), but 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.

[0032] A compound containing a group V element is also disclosed, and the group V element-containing compound is given by 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 = 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 is a group V element selected from As, P, Sb, and Bi; R is C1~C 10 (Selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups) The compounds are as follows: 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; if A=Sb, then Sb(SiH3)3 is excluded. The disclosed compounds may comprise one or more of the following embodiments: • The purity of the compound containing group V elements is >93%; • The purity of the compound containing group V elements is >95%; • The purity of the compound containing group V elements is >98%.

[0033] A method for forming a film containing Si and a group V element on a substrate is also disclosed, and this method is Exposing a substrate to the vapor of a film-forming composition containing a precursor containing Si and a group V element; and A film containing Si and group V elements is formed on the substrate by depositing at least a portion of a precursor containing Si and group V elements onto the substrate using a vapor deposition method. Includes, Precursors containing Si and Group V elements are given 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 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; R is C1~C 10 (Selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups) The compounds are present, but 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 embodiments: • Group V element-containing 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(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 Selected from 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 include 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)( Selected from 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; 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 CVD processes, ALD processes, epitaxy processes, or combinations thereof; The film-forming composition is activated by heating the substrate to a temperature in the range of 200°C to 1000°C, activating a precursor containing Si and a group V element with plasma, or a combination thereof; The step further includes exposing the substrate to a co-reactant; • The co-reactant is activated by plasma; • The co-reactant is not activated by the plasma; The co-reactant is an oxygen-containing gas selected from O2, O3, H2O, H2O2, NO, N2O, NO2, O radicals, alcohols, silanols, amino alcohols, 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, amines, trisilylamines, silazanes, or combinations thereof; • The co-reactant is H2; • The co-reactant is N2; The co-reactant is at least one secondary precursor selected from silanes and polysilanes, alkylsilanes, halosilanes (MCS, DCS, TCS, SiCl4), polyhalopolysilanes, germanes, chlorogermanes, digermanes, polygermanes, halogermanes, phosphines, boranes, or halide-containing gases; • The co-reactant is a diluent gas selected from Ar, He, N2, H2, or a combination thereof; A film containing Si and a group V element is a P-doped silicon-containing film; The process further includes annealing a 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 in powder form; The powder contains one or more of the following: NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials.

[0034] Also, 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 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; R is C1~C 10 (Selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups) A film-forming composition for depositing films is also disclosed, which contains a precursor having Si and a group V element, wherein if A=As, As(SiH3)3 is excluded; if A=P, 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, Sb(SiH3)3 is excluded. The disclosed film-forming composition may comprise one or more of the following embodiments: • Group V element-containing 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(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 Selected from 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 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)( Selected from 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; • 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 are wet film-forming compositions for spin-coating films, comprising a precursor containing Si and a Group V element, disclosed from formula (I), (II), or (III), having at least five Si atoms. The disclosed wet film-forming compositions may comprise one or more of the following embodiments: A precursor containing Si and a group V element from formula (I), (II), or (III) having the lowest volatility is selected to remain in the spin-cast film during the annealing step and decompose in situ; The co-reactant further comprises a polysilane or polysilane mixture having five or more silicon atoms; • Polysilane is cyclopentasilane; • Polysilane is cyclohexasilane; • Contains a solvent; • The spin-cast film is an amorphous or polycrystalline Si film; • The spin-cast film is an amorphous or polycrystalline Si film; • The spin-cast film is an amorphous silicon film; • The spin-cast film is a polycrystalline silicon film.

[0036] A method for forming a Group V element-doped epitaxial Si film on a substrate is also disclosed, and this method is Maintain the substrate at a predetermined temperature near the deposition temperature; Exposure of a substrate to a mixture of vapor from a film-forming composition containing a precursor containing Si and a group V element, and vapor from a co-reactant polysilane; A precursor containing Si and a group V element is deposited on a substrate, and a group V element-doped epitaxial Si film is formed on the substrate by a CVD process; A precursor containing Si and a group V element is a 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 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; R is C1~C 10 (Selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups) The compounds are present, but 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 embodiments: The mixture contains a diluent gas selected from Ar, He, N2, H2, or a combination thereof; • The co-reactant polysilane is germane; • The specified temperature is in the range of 200°C to 1000°C; • The deposition temperature is in the range of 200°C to 1000°C; If A is P, then a Group V element-doped epitaxial Si film is a P-doped epitaxial Si film.

[0037] Notation and Nomenclature The following detailed description and claims utilize several abbreviations, symbols, and terms commonly known in the art. Definitions are typically provided with the first example of each abbreviation, such as stainless steel (SS). Certain abbreviations, symbols, and terms are used throughout the following description and claims, and include the following:

[0038] The following detailed description and claims utilize several abbreviations, symbols, and terms that are commonly known in the art.

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

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

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

[0042] As used herein, “atmospheric pressure” in the text or claims means approximately 1 atmosphere.

[0043] The term "substrate" refers to one or more materials on which a process is performed. A substrate can mean a wafer having one or more materials on which a process is performed. A substrate can be any suitable wafer used in the manufacture of semiconductors, photovoltaics, flat panels, or LCD-TFT devices. A substrate can also have one or more layers of different materials already deposited thereon from previous manufacturing steps. For example, a wafer may 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 may be planar or patterned. A substrate can be an organically patterned photoresist film. The substrate may include a layer of oxides (e.g., ZrO2-based materials, HfO2-based materials, TiO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc.) used as dielectric materials 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 terms “film” or “layer” as used herein refer to the thickness of any material placed on or spread on a surface, and the surface may be a trench or a line. Throughout this specification and the claims, the wafer and any relevant layer thereon are referred to as the substrate.

[0044] The terms “wafer” or “patterned wafer” mean a wafer having a stack of films on a substrate and having at least one top film having topographic features formed in a step prior to the 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 the diameter of the aperture).

[0046] It should be noted that the terms “film” and “layer” may be used interchangeably in this specification. A film may correspond to or be associated with a layer, and a layer may mean a film. Furthermore, as used herein, the terms “film” or “layer” mean any material of a certain thickness that is placed on or spread across a surface, which may range in size from an entire wafer to a trench or line.

[0047] In this specification, the terms “aperture,” “via,” “hole,” and “trench” may be used interchangeably to refer to openings formed in a semiconductor structure.

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

[0049] It should be noted that the terms “deposition temperature” and “substrate temperature” may be used interchangeably in this specification. Substrate temperature may correspond to or be associated with the deposition temperature, and deposition temperature may mean the substrate temperature.

[0050] In this specification, the terms “precursor,” “deposit compound,” and “deposit gas” may be used interchangeably when the precursor is in a gaseous state at room temperature and ambient pressure. It is understood that the precursor may correspond to or be associated with a deposit compound or deposit gas, and that a deposit compound or deposit gas may mean the precursor.

[0051] This specification uses standard abbreviations for elements from the periodic table. It should be understood that elements can be referred to by these abbreviations (for example, Si means silicon, N means nitrogen, O means oxygen, C means carbon, H means hydrogen, Hal means halogen, which are F, Cl, Br, and I).

[0052] The unique CAS registry number (i.e., "CAS") assigned by the Chemical Abstract Service is provided to identify the specific molecule being disclosed.

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

[0054] Note that silicon-containing films such as SiN and SiO are enumerated throughout the specification and claims without providing 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 dioxide (Si n O m ) layers; or mixtures thereof may be included, where k, l, m, and n are in the range of 0.1 to 6 (inclusive). Preferably, silicon nitride is Si with k and I in the range of 0.5 to 1.5 each. k N l More preferably, silicon nitride is Si3N4. In this specification, in the following description, SiN is Si k N l It may be used to represent the containing layer. Preferably, the silicon dioxide is Si where n is in the range of 0.5 to 1.5 and m is in the range of 1.5 to 3.5. n O m More preferably, silicon dioxide is SiO2. In this specification, SiO in the following description refers to Si n O mUsed to represent the 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 dielectric constant dielectric material, such as Black Diamond II or III material by Applied Materials, Inc., which has the formula SiOCH. The silicon-containing film is a Si film 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 contain dopants of groups III, IV, V, and VI, 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 specifying their appropriate stoichiometry (i.e., SiO, SiO2, Si3N4). The layers may include pure (Si) layers, carbide (Si) layers, etc. O C p ) layer, nitride (Si k N l ) layer, oxide (Si n O m ) may include layers or mixtures thereof, where k, l, m, n, o, and p are in the range of 1 to 6 (including the endpoint). For example, silicon dioxide is Si n O m The values ​​are such that 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 dielectric constant dielectric material such as Black Diamond II or III material by Applied Materials, Inc. Alternatively, the silicon-containing layer mentioned 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; "Et" refers to an ethyl group; "Pr" refers to any propyl group (i.e., n-propyl or isopropyl); "iPr" refers to an isopropyl group; "Bu" refers to any butyl group (n-butyl, isobutyl, tert-butyl, sec-butyl); "tBu" refers to a tert-butyl group; "sBu" refers to a sec-butyl group; "iBu" refers to an isobutyl group; "Ph" refers to a phenyl group; "Am" refers to any amyl group (isoamyl, sec-amyl, tert-amyl); "Cy" refers to a cyclic hydrocarbon group (cyclobutyl, cyclopentyl, cyclohexyl, etc.); "Ar" refers to an aromatic hydrocarbon group (phenyl, xylyl, mesityl, etc.); and TMS refers to a trimethylsilyl-SiMe3 group.

[0057] In this specification, a range may be expressed as from approximately one specific value to and / or approximately another specific value. When expressed in such a range, another embodiment should be understood as from one specific value to and / or the other specific value, together with all combinations within the said range. Any range enumerated herein, whether or not the term “inclusively” is used, encompasses its endpoints (i.e., x = 1 to 4 or x is in the range of 1 to 4 includes x = 1, x = 4, and any number in between).

[0058] Any reference herein to “one embodiment” or “a certain embodiment” means that certain features, structures, or characteristics described in relation to that embodiment may be included in at least one embodiment of the present invention. The phrase “in one embodiment” in various places herein does not necessarily refer to that embodiment, nor do separate or alternative embodiments necessarily exclude other embodiments from each other. The same applies to the term “realization.”

[0059] As used herein, the term “exemplary” means an example, case, or illustration. No embodiment or design described herein as “exemplary” should be interpreted as necessarily being preferable or superior to any other embodiment or design. Rather, the use of the term “exemplary” is intended to present a concrete concept.

[0060] Furthermore, the term "or" is intended to mean inclusive "or" rather than exclusive "or". That is, unless otherwise specified or it is clear from the context, "X adopts A or B" is intended to mean any reasonable inclusive rearrangement. That is, if X adopts A, X adopts B, or X adopts both A and B, "X adopts A or B" is satisfied under any of the above cases. In addition, the articles "a" and "an" used in this application and the attached claims should generally be interpreted as meaning "one or more" unless otherwise specified or it is clear from the context that they refer to a singular form.

[0061] The aforementioned and various other aspects, features, and advantages of the present invention, as well as the invention itself, can be better understood by referring to the subsequent detailed description of the invention when considered in conjunction with the following drawings. The drawings are presented for illustrative purposes only and are not intended to limit the invention. [Brief explanation of the drawing]

[0062] [Figure 1] Figure 1 is the 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). [Figure 2] Figure 2 is the GC chromatogram of the reaction mixture of P(TMS)3 + 3MCS (monochlorosilane, i.e., SiH3Cl) reacted at 90°C for 44 hours (Example 4). [Figure 3] Figure 3 is the GC chromatogram of the reaction mixture of As(TMS)3+6MCS reacted at 60°C for 24 hours (Example 5). [Figure 4] Figure 4 is the GC chromatogram of the Sb(TMS)3 + 10MCS reaction mixture reacted at 60°C for 24 hours (Example 8). [Modes for carrying out the invention]

[0063] A group V element-containing film-forming composition comprising a group V element-containing precursor containing inorganic silyls and polysilyls, a method for synthesizing the same, and a method for using the same to deposit a group V element-containing film are disclosed.

[0064] The Group V element-containing precursors disclosed herein 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 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; R is C1~C 10 (Selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups) The formulas are as follows: 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; if A=Sb, then Sb(SiH3)3 is excluded.

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

[0066] Examples of precursors of this 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 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 this 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(In these formulas, a = 1 to 6; m = 1 to 3; and A is a group V element selected from P, As, Sb, or Bi), but 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 = Me, examples of precursors of this 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), and 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 precursors of this disclosure are 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~C 10 The group is selected from the group consisting of linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups, but if A=P, P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) are excluded.

[0069] Preferably, when m=3, the Group V element-containing precursor of this disclosure is A(Si a H 2a+1 )3(In the formula, a = 1 to 6, A is a group V element selected from P, As, Sb, or Bi, and R is C1 to C10 The group is selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups, but when A=As, n>1; when A=P, P(Si2H5)3 is excluded; and when A=Sb, Sb(SiH3)3 is excluded.

[0070] The Group V element-containing precursors of this 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 represented by formulas (I) to (III) of this disclosure is a halosilyl compound or halopolysilyl compound (X-Si) that follows the following general reaction. n H 2n+1 This includes a dehalosilylation (DXS) pathway between ) and A(SiR3)3, which is a 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) (In the formula, 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 (Selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups).

[0072] The synthesis method disclosed herein involves A(SiR3)3 and halo(poly)silane(X-Si a H 2a+1 The process includes optionally adding a solvent to bring the two together in a ratio of halo(poly)silane to A(SiR3)3 in the range of 1 to 100 equivalents to 100 to 1 equivalent, preferably 1 to 20 equivalents to 20 to 1 equivalent, where the halo(poly)silane is preferably chloro(poly)silane. The solvent is A(SiR3)3 and halo(poly)silane (X-Si a H 2a+1 The halo(poly)silane to A(SiR3)3 is inert to both reactants and is selected from alkanes or aromatic solvents such as pentane, hexane, heptane, benzene, toluene, xylene, or haloalkylsilanes or mixtures thereof, in the form of 0-99% by weight of the reactant or starting material, 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 undiluted or dissolved in a solvent using an airtight manifold, either by direct addition of liquid or condensation of undiluted vapor. The mixture of reactants is then stirred, typically for 1-168 hours, to form the reaction mixture. The product can then be separated from the reaction mixture by solvent stripping and / or fractional distillation or by other suitable means known in the art. The isolated product can then be purified to the target purity by distillation, for example, in either batch or continuous order.

[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 in the range of -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 method of this disclosure may be carried out stepwise, and silyl groups of various sizes may be substituted sequentially, such as in a two-step or three-step reaction.

[0075] The two-step reaction of the present disclosure between a halosilyl or halopolysilyl compound and 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 to 6, and b = 1 to 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 (Selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups).

[0076] The three-step reaction of a halosilyl or halopolysilyl with a tris(trialkylsilyl) derivative of A according to this disclosure 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 to 6, a = 1 to 6, c = 1 to 6; A = As, P, Sb, Bi; X = Cl, Br, I; R is C1~C 10 (Selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups).

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

[0078] The mixed reactions of halosilyl or halopolysilyl with tris(trialkylsilyl) derivatives of A according to this disclosure have the following general reactions: 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 to 6, b = 1 to 6, c = 1 to 6; x = 0 to 3, y = 0 to 3, z = 0 to 3, and x + y + z = 1 to 3; A = As, P, Sb, Bi; X = Cl, Br, I; R is C1~C 10 (Selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups).

[0079] In one embodiment, the synthetic method of the present disclosure for synthesizing the group V element-containing precursors of the present disclosure represented by 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 And, a tris(trialkylsilyl) derivative of A (A=As, P, Sb, or Bi), A(SiR3)3 (R is C1~C) 10 This is a dechlorosilylation (DCS) pathway between a linear, branched, or cyclic alkyl, alkenyl, or alkynyl group (selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups).

[0080] The synthesis reactions of this disclosure may be carried out in batch form. 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 is preferred when only partial substitution of the -SiR3 group on A is desired.

[0081] The synthetic reactions of this disclosure can be carried out in a continuous mode in which each reagent is supplied in a continuous flow for reaction. A continuous mixing system may be used to facilitate contact of the reagents. Although the reaction is not expected to produce solid byproducts, a filtration step may be added after synthesis to remove potential solid byproducts as a precaution. Volatile byproducts of the reaction may be continuously removed so that the reaction proceeds to completion or multi-step transformation. This is an inherent advantage of the synthetic method of this disclosure, which produces little to no solid byproducts. It is understood that substituting chlorosilane reagents with bromosilane does not result in significant deviations. Chlorosilane is more convenient for reasons of availability.

[0082] The synthesis method disclosed herein has the following unique advantages. • Easily available starting materials: Existing synthesis methods use reagents such as KPH2 and P(SnMe3)3, which are either commercially difficult to obtain or require new preparation. In contrast, the synthesis method of this disclosure uses P(TMS)3, As(TMS)3, or Sb(TMS)3, which are commercially available in high purity bulk, as starting materials. 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 synthetic method of this disclosure can be a one-step synthesis when introducing only one type of polysilyl group. Most existing synthetic methods are multi-step reactions that require the preparation of mono- or disilylphosphines such as SiH3PH2, Si2H5PH2, and LiAlH[P(SiH3)2]3, arsines, etc., in the first step and then isolation. In contrast, the synthetic method of this disclosure is a one-step, one-reactor process that does not necessarily require the isolation of by-products during synthesis. The synthesis method described herein is carried out under mild reaction conditions. Due to the instability of the starting materials, existing synthesis methods almost always require the reaction to be carried out at low temperatures while carefully controlling the rate of addition of the reagents and / or the melting rate of the mixture. In contrast, the synthesis method described herein is carried out at temperatures slightly above ambient temperature, such as in the range of room temperature to 100°C. The synthesis method of this disclosure has few side reactions and high yield. The DHS route of this disclosure yields relatively high yields as a result of fewer side reactions, and subsequent separation and purification processes are facilitated. The synthetic methods described herein involve little to no salt formation. This is known to promote the degradation of analog molecules, such as N-based analogs with a trisilylamine (TSA) skeleton.

[0083] The Group V element-containing film-forming precursor of the present disclosure, synthesized by the synthesis method of the present disclosure, can be used to vapor-phase deposit a Si-containing film having a Group V element dopant in silicon by CVD, PECVD, ALD, PEALD, fluid CVD, HW-CVD, epitaxy, etc.

[0084] P and As compounds, especially their inorganic derivatives, such as As(Si x H y )3, P(Si x H y )3 (wherein x and y may be the same or different at each silyl moiety, and y = 2x + 1) can be conveniently used as dopants in silicon. In some applications, doping beyond the solubility limit of the dopant in silicon is strongly required, 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 approximately 450°C. The group V element-containing precursors of this 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 this disclosure are typically supplied in a high-purity container made of stainless steel, carbon steel, or aluminum, which is pre-dried to a residual H2O level of less than 100 ppb and optionally passivated to limit the degradation of the precursors within it over time. The passivation process typically involves exposing the high-purity container to a silylate, which may be the precursor of interest itself, or a silane or polysilane.

[0086] The Group V element-containing precursors of this disclosure preferably have a purity of over 90% w / w (i.e., 93.0% w / w to 100.0% w / w), preferably over 95% w / w (i.e., 98.0% w / w to 100.0% w / w), more preferably over 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 less than 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 this disclosure can be purified by recrystallization, sublimation, distillation, and / or gas-liquid passage through a suitable adsorbent such as a molecular sieve.

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

[0088] When the vapor pressure of the precursor at a container temperature in the range of 0°C to approximately 150°C is typically >50 torr, preferably >300 torr, the vapor of the Group V element-containing precursor of this disclosure can be supplied directly to the process chamber without a carrier gas.

[0089] For Group V element-containing precursors of the present disclosure having a low vapor pressure, the vapor of the Group V element-containing precursor is supplied to the process chamber together with a carrier gas by either a bubbler, vapor suction, 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 can also be removed by bubbling with the carrier gas. The carrier gas and precursor are then introduced into the process chamber as 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 container containing the Group V element-containing precursor of this disclosure may be heated or cooled to a temperature such that the precursor has a sufficient and appropriate vapor pressure. The container may be maintained at a temperature in the range of approximately 0°C to approximately 200°C, for example. It will be apparent to those skilled in the art that the temperature of the container may be adjusted as known to control the amount of precursor vaporized.

[0091] A process chamber is any enclosure chamber within the device in which the deposition method is carried out, and can be, for example, a parallel plate reactor, a cold wall reactor, a hot wall reactor, a single wafer reactor, a multi-wafer reactor, or any other type of deposition system under conditions suitable for causing precursor reaction and deposition film formation. It will be apparent to those skilled in the art that any of these process chambers can be used in either ALD or CVD deposition processes.

[0092] A process chamber comprises one or more substrates on which a film is deposited. A substrate is generally defined as the material on which the process is carried out. The substrate can be any suitable substrate used in the manufacture of semiconductors, photovoltaics, flat panels, or LCD-TFT devices. Examples of suitable substrates include wafers such as silicon, silica, glass, and GaAs wafers. A wafer may also have one or more layers of different materials deposited on it from previous manufacturing steps. For example, a wafer may contain a dielectric layer or a 3D NAND layer. Furthermore, a wafer may contain 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, a wafer may contain copper layers, noble metal layers (e.g., platinum, palladium, rhodium, gold). A wafer may contain barrier layers such as manganese or manganese oxide. Plastic layers may also be used. The layers may be planar or patterned. The deposition process of this disclosure allows the patterned layers to be deposited directly onto a wafer or directly onto one or more layers on a wafer when the patterned layers are formed on a substrate. The patterned layers may be alternating layers of two specific layers, such as SiO and SiN used in 3D NAND.

[0093] The end-use of the substrate is not limited to the present invention, but this technology may be particularly advantageous for substrates of the type such as silicon wafers, glass wafers and panels, beads, powders and nanopowders, monolithic porous media, printed circuit boards, and plastic sheets. Exemplary powder substrates include powders used in rechargeable battery technology. A non-limited 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 within the process chamber are maintained at conditions suitable for vapor-phase deposition such as ALD or CVD. In other words, after introducing the vaporized Group V element-containing material of this disclosure into the chamber, the conditions within the chamber are such that at least a portion of the precursor deposits onto the substrate to form a layer. For example, the pressure in the reactor or the deposition pressure is set to approximately 10 as needed for each deposition parameter. -3 Torr ~ about 500 torr, preferably about 10 -2 The torr can be maintained at approximately 500 torr, more preferably at approximately 1 torr to 100 torr. Similarly, the temperature inside the reactor or the deposition temperature can be maintained at room temperature to approximately 1000°C, preferably at 200°C to 800°C. Those skilled 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 it.

[0095] The temperature required for optimal film growth can be controlled by controlling the temperature of the substrate holder. Apparatus used to heat the substrate is known in the art. The substrate is heated to a temperature sufficient to obtain a desired film with a desired physical state and composition at a sufficient growth rate. A non-limiting exemplary temperature range in which the substrate can be heated includes approximately 200°C to approximately 800°C. When a plasma deposition process is used, the deposition temperature is preferably below 500°C. Alternatively, when a thermal process is performed, the deposition temperature may be in the range of 200°C to approximately 800°C.

[0096] Alternatively, the substrate may be heated to a temperature sufficient to obtain a desired deposited film having the desired physical state and composition at a sufficient growth rate. The substrate temperature can be maintained 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 this disclosure, other precursors or co-reactants, such as, but not limited to, H2, silanes, polysilanes (Si2-Si6, Si5 and Si6 in linear, branched, or cyclic forms), alkylsilanes (such as monomethylsilane), halosilanes (Cl-SiH3, Cl2SiH2, I2-SiH2, Cl3SiH 、 Gases containing phosphates such as SiCl4, polyhalopolysilanes (Si2Cl6, Si2HCl5, Cl-Si2H5, etc.), Germanine, chlorogermane, digermane, polygermane, halogermane, phosphine, borane (B2H6, etc.), diborane, halide (HCl, Cl2, HBr, etc.); nitrogen-containing gases (NH3, N2, N2 / H2, and NH3, N2 and NH3, NH3 and N2H4, NO, N2O, amines, trisilylamines, silazanes, etc., or combinations thereof); oxygen-containing gases (O2, O3, H2O, H2O2, NO, N2O, NO2, oxygen radicals, alcohols, silanols, amino alcohols, carboxylic acids, paraformaldehyde, etc., and combinations thereof) can also be introduced into the process chamber.

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

[0099] Furthermore, the co-reactant may be treated with plasma, and when the precursor or reactant is treated with plasma to decompose it into its radical form, 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 film. 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, or mixtures thereof. For example, the plasma can be generated with a power in the range of about 10W to about 1000W, preferably about 50W to about 500W. The plasma can be generated and present within the reactor itself. Alternatively, the plasma may generally be present at a location away from the reactor, for example, in a remotely installed plasma system. Those skilled in the art will recognize suitable methods and apparatus for such plasma treatment.

[0100] For example, a co-reactant can be introduced into a direct plasma reactor that generates plasma in a reaction chamber, and a plasma-treated reactant can be produced in a process chamber. An exemplary direct plasma reactor is the Titan® PECVD system from Trion Technologies. The co-reactant may be introduced into and held in the process chamber before plasma treatment. Alternatively, plasma treatment may be performed simultaneously with the introduction of the precursor or reactant. The in-situ plasma is typically a 13.56 MHz RF inductively coupled plasma generated between a showerhead and a substrate holder. The substrate and showerhead may be electrodes to which power is supplied depending on whether or not a cation bombardment occurs. Typical applied power in an in-situ plasma generator is about 30 W to about 1000 W. Preferably, power of about 30 W to about 600 W is used in the method of this disclosure. More preferably, power is in the range of about 100 W to about 500 W. Dissociation of a co-reactant using in-situ plasma is typically less than that achieved using a remote plasma source at the same power input, and therefore the reactant dissociation is not as efficient as in a remote plasma system. 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 processes the co-reactant before it enters the process chamber.

[0102] The deposition process may be selective or non-selective to a particular surface.

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

[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 vapor deposition methods include CVD and ALD. Exemplary CVD methods include thermal CVD, plasma-enhanced CVD (PECVD), pulsed CVD (PCVD), low-pressure CVD (LPCVD), sub-atmospheric CVD (SACVD), atmospheric pressure CVD (APCVD), hot-wire CVD (also known as HWCVD, cat-CVD, where the hot wire functions 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 an epitaxial film or an amorphous film containing Si and the dopant element of the compound recited in the claims, and optionally also containing Ge and / or other co-dopants.

[0105] In the ALD process, depending on the ALD conditions in the chamber, the Group V element-containing film-forming composition adsorbed or chemisorbed on the substrate surface can react to form a film on the substrate. In some embodiments, the applicant believes that a co-reactant that is plasma-treated 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 sequentially introduced into the reactor (ALD). The process chamber can be purged with an inert gas between each introduction of the Group V element-containing precursor, additional precursors, and the co-reactant. Another example is to continuously introduce the co-reactant while sequentially activating the co-reactant with plasma, and introduce the Group V element-containing precursor in pulses, provided that the Group V element-containing precursor and the non-activated co-reactant do not substantially react under the temperature and pressure conditions of the chamber (CWPEALD).

[0107] Each pulse of the Group V element-containing precursor of the present disclosure can be continued for a time in the range of about 0.01 seconds to about 120 seconds, alternatively about 1 second to about 80 seconds, alternatively about 5 seconds to about 30 seconds. The co-reactant may also be introduced into the reactor in pulses. In such embodiments, each pulse can be continued for a time in the range of about 0.01 seconds to about 120 seconds, alternatively about 1 second to about 30 seconds, alternatively about 2 seconds to about 20 seconds. In another alternative, the vaporized Group V element-containing precursor and co-reactant can be sprayed simultaneously without mixing from different sectors of a showerhead, under which a susceptor holding a plurality of wafers rotates (spatial ALD).

[0108] Depending on the specific process parameters, deposition can be carried out over various times. Generally, deposition can be continued for the time necessary to produce a film having the required properties. Typical film thicknesses can vary from a few angstroms to hundreds of microns, typically 2 - 100 nm, depending on the specific deposition process. The deposition process can also be carried out the number of times necessary to obtain the desired film.

[0109] The Group V element-containing precursor and co-reactant of the present disclosure can be introduced into the reactor either simultaneously (CVD), sequentially (ALD), or in any different combination 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, and then this can be introduced into the reactor in mixture form (CVD, thermal CVD, or epitaxy). Another example is the continuous introduction of the co-reactant and the pulsed introduction of the Group V element-containing precursor of the present disclosure (pulsed CVD).

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

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

[0112] The film deposited using the deposition method of this disclosure may be a film containing p-doped Si and a group V element.

[0113] The film deposited using the deposition method of this disclosure may be a group V element-doped silicon layer, such as a P-doped silicon layer.

[0114] The Group V element-containing film-forming compositions of this 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 this case, a formulation containing the compounds of this disclosure is coated onto a substrate and then annealed to obtain a thin film.

[0115] The Group V element-containing film-forming compositions of this disclosure are particularly useful as doping components in formulations intended for the production of amorphous and polycrystalline Si films. Such formulations typically comprise a large polysilane or mixture of polysilanes (e.g., cyclopentasilane, cyclohexasilane) having five or more silicon atoms and a solvent. After coating a substrate with the formulation, the film is treated to obtain a silicon film. In such spin-coating applications, the selected precursor must have the lowest volatility so that it remains on the spin-coated film during the annealing step and decomposes in situ. For such applications, a group of precursors typically having at least five Si atoms is suitable.

[0116] The treatment typically involves heating (200–1000°C) and / or light / UV exposure. In such formulations, the group V element-containing compounds of this disclosure may be added in amounts of 0.01%–50% (by weight) to obtain a doped silicon film.

[0117] Formulations containing Group V element precursors of this disclosure can also be used to produce silicon oxide films doped by any of the wet coating methods described above by using oxidative curing after surface coating. 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 includes a two-step process: 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, a completely inorganic and low-volatility precursor, preferably A(Si), is preferred. x H 2x+1 It is advantageous to use a precursor selected from )3 (where x is 2 or greater and A = As or P). [Examples]

[0118] The following non-limiting embodiments are provided to further illustrate embodiments of the present invention. However, the embodiments are not intended to be exhaustive or to limit the scope of the invention as 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% P(TMS)3 solution in hexane while magnetically 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 P(TMS)2(Si3H7) in a yield of 68%.

[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 an inert atmosphere, and then 75 g of monochlorotrisilane MCTS was slowly added while magnetically 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 is the GC chromatogram of the P(TMS)3 + 7MCTS reaction mixture reacted in hexane at 68 °C for 24 hours.

[0121] Example 3. Synthesis of (TMS)P(SiH3)2 5 g of 10 wt% P(TMS)3 in hexane was placed in a 60 mL stainless steel container. 2.6 g of monochlorosilane MCS was cryotrapped into the container. The reaction mixture was thawed and shaken at 150 rpm in a sealed container at 75°C for 24 hours. During this time, all P(TMS)3 was converted to most P(TMS)(SiH3)2 in a 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 container. 6.9 g of monochlorosilane MCS was cryotrapped into the container. The reaction mixture was thawed and shaken at 150 rpm at 90°C for 48 hours in a sealed container. During this time, all P(TMS)3 was converted to most P(SiH3)3 in 85% yield.

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

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

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

[0126] Example 7. Synthesis of Sb(Si3H7)(TMS)2 Sb(Si3H7)(TMS)2 can be synthesized in a 72% yield by reacting 2 g of Sb(TMS)3 and 7 g of MCTS at room temperature for 1 day with vigorous magnetic stirring. 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 container. 9 g of monochlorosilane MCS was cryotrapped into the container. The reaction mixture was thawed and shaken at 60 °C and 150 rpm for 24 h in a sealed container. During this time, most of Sb(SiH3)(TMS)2 was obtained in a 23% yield. Figure 4 is the GC chromatogram of the reaction mixture of 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% P(TMS)3 solution in hexane was placed in 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 in a sealed container at 60°C for 24 hours. During this time, P(Si2H5)3 was formed in a yield of 22%.

[0129] Example 10. Isolation of P(SiH3)3 380 g of the synthesis mixture, containing the product profile as 26% P(SiH3)3 in a TMS-Cl solution, was placed in a 500 mL round-bottom flask in a glove box. Standard fractional distillation was then performed. After removing volatile components at 55–70°C, the main cut component with a vapor phase temperature in the range of 115–125°C was recovered at ambient pressure to obtain 75 g of P(SiH3)3 with a purity of 98%. This corresponds to an overall yield of 76%. Further distillation or distillation with higher separation efficiency is expected to preferably achieve a purity of over 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 container at 30 wt% TMS-Cl. 2.0 g of MCTS was added to the container. The reaction mixture was shaken at 150 rpm in a sealed container at 75°C for 24 hours. During this time, 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 in a container. The reaction mixture was thawed and vigorously stirred at 75°C at 400 rpm for 24 hours. During this time, all of the P(TMS)3 was converted to most of the P(SiH3)(TMS)2.

[0132] Approximately 25% by weight of P(SiH3)(TMS)210 g in TMS-Cl was placed in a 60 mL stainless steel container. 2.4 g of MCDS was added to the container. The reaction mixture was shaken at 150 rpm in a sealed container at 60°C for 40 hours. During this time, P(SiH3)(Si2H5)2 was formed as the main product.

[0133] Virtual Example 3. CVD of a P-doped Si layer using precursor P(Si3H7)3 An attempt is made to deposit a P-doped Si layer on a Si(100) substrate. P(Si3H7)3 vapor is introduced into a deposition reactor (heated to approximately 500°C) at a flow rate of 10 sccm and a pressure of approximately 1 to 20 torr for 10 to 20 minutes. During this time, a polycrystalline P-doped silicon film with a thickness of 500 to 1500 Å is obtained. SEM images of the obtained P-doped silicon film can be obtained. An energy-dispersive X-ray spectroscopy (EDAX) detector can be used for elemental analysis. AFM, XRD, and ellipsometry measurements may be performed on the 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 may be used to characterize the deposited film.

[0134] Virtual Example 4: Thermal CVD of a high-quality P-doped Si layer on a Si(100) wafer using the precursor P(SiH3)2(Si3H7). A Si(100) substrate, pre-etched with dilute HF acid and properly conditioned (rinsed and dried), is loaded into a deposition chamber, followed by an H2 bake at 800-1000°C with a flow rate of 50-120 slm. The substrate and chamber are then brought to equilibrium at 400-600°C with a back pressure of 20-50 torr. Pure H2 gas is then blown through a liquid precursor P(SiH3)2(Si3H7), supplying a vapor of the P(SiH3)2(Si3H7) / H2 mixture to the reactor 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 is deposited on the Si(100) wafer. The absence of hydrogen residue can be confirmed by RBS.

[0135] Virtual Example 5: High-throughput thermal CVD of P-doped Si films on Si(100) wafers using precursor P(SiH3)(Si3H7)2 A Si(100) substrate, pre-etched with dilute HF acid and properly conditioned (rinsed and dried), is loaded into a deposition chamber, followed by an H2 bake at 800-1000°C with a flow rate of 50-120 slm. The substrate and chamber are then brought to equilibrium at 550°C with a back pressure of 50 torr. Pure H2 gas is then blown through a liquid precursor P(SiH3)2(Si3H7) at equilibrium at approximately 75°C, and then blown into trisilane at room temperature, which is sent to a mixing chamber at approximately 100°C. Subsequently, a vapor of the P(SiH3)(Si3H7)2 / Si3H8 / H2 mixture is 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 is deposited on the Si(100) wafer.

[0136] The subject matter described herein may be described in relation to exemplary implementations for handling one or more computing application features / operations for computing applications having user interaction components, but the subject matter is not limited to such specific embodiments. Rather, the techniques described herein may be applied to any preferred type of user interaction component execution management method, system, platform, and / or apparatus.

[0137] Those skilled in the art will understand that many additional modifications to the details, materials, steps, and arrangements of the parts described and illustrated herein to illustrate the nature of the present invention can be made within the principles and scope of the invention as expressed in the appended claims. Therefore, the present invention is not intended to be limited to the examples and / or specific embodiments of the appended drawings.

[0138] While embodiments of the present invention have been 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 not 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 limited only by the subsequent claims, which include all equivalents of the subject matter of the claims.

Claims

1. A method for synthesizing compounds containing group V elements, A (SiR ３ ) ３ X-Si ａ H ２ａ＋１ ,X-Si ｂ H ２ｂ＋１ , and X-Si ｃ H ２ｃ＋１ Contacting one, two, or three types of halo(poly)silane selected from the group consisting of the above, either in succession or as a mixture, and The following is the overall step-by-step response: 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 ｃ H ２ｃ＋１ →A(Si ａ H ２ａ＋１ )(Si ｂ H ２ｂ＋１ )(Si ｃ H ２ｃ＋１ )+X-SiR ３ ; Therefore, Alternatively, 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 Therefore, A (SiR ３ ) ３ Dehalosilylation is performed 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 ) To form, These formulas include, 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 is a group V element selected from As, P, Sb, and Bi; R is C １ ~C １０ A method selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups.

2. A solvent selected from alkanes, aromatics, or haloalkylsilane solvents, or mixtures thereof, is added, and A(SiR ３ ) ３ The method according to claim 1, wherein the ratio of the solvent to is 0 to 99% by weight.

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

1.

4. The method according to claim 1, wherein X is Cl.

5. The aforementioned halo(poly)silane is Cl-SiH ３ , Cl-Si ２ H ５ , or Cl-Si ３ H ７ The method according to claim 1.

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

7. To isolate the group V element-containing compound by separating the solvent and reaction product; and Purifying the aforementioned Group V element-containing compound; The method according to any one of claims 1 to 6, further comprising:

8. The method according to 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, wherein the process is a batch process.

10. The method according to any one of claims 1 to 6, wherein the overall 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(SiR ７ )(Si ２ H ３ ), P(Si ２ H ３ ), P(SiR ７ )(Si ３ H ７ ), P(Si ３ H ３ ), As(SiH ３ ), As(SiR ３ )(SiH ３ ), As(SiR ２ )(SiH ３ ), As(SiR ２ )(Si ３ H ３ ), As(SiR ２ )(Si ５ H ２ ), As(SiR ３ )(Si ２ H ２ ), As(Si ５ H ２ ), As(SiR ５ )(Si ３ H ３ ), As(SiR ３ )(Si ７ H ２ ), As(SiR ３ )(Si ２ H ３ ), As(Si ７ H ３ ), Sb(SiH ７ ), Sb(SiR ３ ), Sb(SiR ３ ) ３ ,Sb (SiR) ３ )(SiH ３ ) ２ ,Sb (SiR) ３ ) ２ (SiH) ３ ),Sb (SiR ３ )(Yes ２ H ５ ) ２ ,Sb (SiR) ３ ) ２ (Yes) ２ H ５ ),Sb (Si ２ H ５ ) ３ ,Sb( ｳiｲ 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 8 ７ )、ｳbb(3iiｨ ３ )(3i ２ 8 ５ ) ) ２ 、″b(″iiｨ ３ )(3i ２ 8 ５ )(3i ３ 8 ７ )、ｳbb(3iiｨ ３ )(3i ３ 8 ７ ) ) ２ 、ｳbbii ２ 8 ５ ) ) ２ (3i) ３ 8 ７ ), or Sb(Si ２ H ５ ) (Si ３ H ７ ) ２ The method according to any one of claims 1 to 5, wherein R in these formulas is selected from Me, Et, nPr, iPr, tBu, nBu, iBu, or sBu.

12. When R is Me, the V-group 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, selected from the following.

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 H ５ ), P(TMS) ２ )(Si ２ H ２ H ５ ), P(Si ２ H ５ ), P(TMS)(Si ３ H ３ H ７ ), P(TMS) ２ )(Si ２ H ３ H ７ ), P(Si ３ H ７ ), P(TMS)(SiH ３ )(Si ３ H ２ H ５ ), P(TMS)(SiH ３ )(Si ３ H ７ ), P(SiH ３ )(Si ２ H ２ H ５ ), P(SiH ３ )(Si ２ H ３ H ７ ), P(SiH ３ )(Si ２ H ５ ), P(SiH ２ )(Si ３ H ２ H ５ )(Si ３ H ７ ), P(SiH ３ )(Si ３ H ７ ), P(Si ２ H ２ H ５ )(Si ２ H ３ H ７ ), and P(Si ２ H ５ )(Si ３ H ７ ) ２ Selected from any of claims 1 to 6 The method described in any one of the items.

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