Inorganic silyl and polysilyl derivatives of group V elements, a method for synthesizing the same, and a method for using the same for deposition

Abstract

A precursor containing a group V element, a method for synthesizing the same, and a method for using the same in film deposition are disclosed. The precursor is (SiR3)3-mA(SiaH2a+1)m, (SiR3)3-n-pA(SiaH2a+1)n(SibH2b+1)p or A(SiaH2a+1)(SibH2b+1)(SicH2c+1), wherein a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c; m = 1 to 3; n = 1 to 2; p = 1 to 2; n + p = 2 to 3; A = As, P, Sb, Bi; and R is selected from C1 to C10, linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups. Synthesis methods include one-step, two-step, or three-step reaction(s) between halo(poly)silane(s) and a tris(trialkylsilyl) derivative of A, or a one-pot mixed reaction between a mixture of two or three halo(poly)silanes and a tris(trialkylsilyl) derivative of A. Deposition methods include CVD, PECVD, ALD, PEALD, flow CVD, HW-CVD, epitaxy, etc.

Description

Technology Field

[0001] Cross-reference of related applications

[0002] This application claims the benefit of priority of U.S. Provisional Application No. 63 / 293,348 filed December 23, 2021, the entire contents of which are incorporated herein by reference.

[0003] The present invention relates to a Group V element-containing precursor, a method for synthesizing the same, and a method for using the same in semiconductor film deposition, specifically, the following general chemical formula:

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

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

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

[0007] (Here,

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

[0009] m = 1 to 3 and;

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

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

[0012] R is C1 to C 10The invention relates to a Group V element-containing precursor having a linear, branched, or cyclic alkyl, alkenyl, or alkynyl group; a synthesis method comprising a one-step, two-step, or three-step reaction(s) between a halo(poly)silane(s) and a tris(trialkylsilyl) derivative of A, or a one-pot mixed reaction between a mixture of two or three halo(poly)silanes and a tris(trialkylsilyl) derivative of A; and a method for depositing Si and a Group V element-containing film comprising CVD, PECVD, ALD, PEALD, flow CVD, HW-CVD, epitaxy, etc. Background Technology

[0013] Thin films containing group V elements are used in various applications, including p-doped Si or SiGe semiconductor channel and contact layers, such as solid-state transistors, non-volatile phase-change memory (PCM), solar cells, III-V compounds, and optical storage materials. III-V compound semiconductors can be used in many different applications, including transistors, optoelectronics, and other applications, for example, bipolar transistors, field-effect transistors, lasers, IR detectors, LEDs, broad-band gap semiconductors, quantum well or quantum dot structures, solar cells, and monolithic microwave integrated circuits.

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

[0015] Some group V element-containing compounds (or V compounds) have been made using silyl and polysilyl ligands, namely P(SiH3)3, P(Si2H5)3, and As(SiH3), etc. The use of these compounds for thin film deposition processes has been disclosed for P(SiH3)3 for epitaxial applications as an inductor (see reference) by forming interconnected III-V-(IV)3 "building blocks" that result in a highly stable crystalline structure with average diamond-like symmetry.

[0016] Related prior art includes the following.

[0017] Tice et al. (Dalton Trans., 2010, 39(19), 4551-4558) disclose that P(SiH3)3 is synthesized by P(SnMe3)3 + 3 SiH3Br → (SiH3)3P + 3 Me3SnBr.

[0018] Amberger et al. (Angew. Chem. Int. Ed., 1962, 1, 52) disclose that (SiH3)3P is synthesized in approximately 55% yield by 3 KPH2 + 3 SiH3Br → P(SiH3)3 + 2 PH3 + 3 KBr.

[0019] Amberger et al. (Angew. Chem., 1962, 74, 293) disclose that under mild conditions, (SiH3)3As is synthesized and isolated in approximately 50% yield from the reaction 3 KAsH2 + 3 SiH3Br → As(SiH3)3 + 2 AsH3 + 3 KBr.

[0020] Amberger et al. (Zeitschrift fuer Naturforschung 1963, 18b 157) also disclose the preparation and characteristics of trisilylstibin by reacting Li3Sb + SiH3Br in ether at low temperature and then isolating the light material to produce 77% Sb(SiH3)3.

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

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

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

[0024] Drake et al. (J. Chem. Soc. A, 1971, 13, 2246) disclose that a reactant between P(SiH3)3 and LiAlH4 is formed as one of the products (e.g., LiAlH[P(SiH3)2]3 + Si2H5Br → Si2H5-P(SiH3)2).

[0025] Drake et al. (Inorg. Nucl. Chem. Letters, 1968, Vol. 4, pp361-363) disclose that monobromogerman reacts with trisilylphosphine to provide an 'exchange,' leading to the formation of trigermylphosphine. Monobromosilanes react with KMH2 (M = P, As, Sb) to provide a trisilyl that is not a monosilyl derivative, and monoiodosilanes react with disilylamines to provide a trisilyl species.

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

[0027] 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 through the redistribution reaction of monosilyl- or monogermyl-phosphine, including SiH3PH2, Si2H5PH2, SiH3PH2 / Si2H5PH2, and GeH3PH2, which are promoted by BX3, B2H6, and B5H9.

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

[0029] Yang et al. (Chem. Mater. 2014, 26, 14, 4092-4101) disclose that an Al-P(SiH3)3 intermediate containing an Al-PSi3 core is formed through a low-temperature reaction between P(SiH3)3 and an Al atomic beam (recently confirmed that this can be deposited and matched on a Si(100) lattice), thus presenting a practical route for growing III-V materials on group IV semiconductors.

[0030] Watkins et al. (J. Am. Chem. Soc. 2011, 133, 40, 16212-16218) disclose the fabrication, characterization, and theoretical simulation of a tetragonal strained Al-PSi3 core grown on Si (100).

[0031] Chizmeshya et al. (ECS Transactions, 2012, 50(9), 623-634) disclose a similar application in which intermediates having an Al-PSi3 core are formed using molecular beam epitaxy (MBE) technology at < 600°C and subsequently incorporated into diamond-shaped Group IV materials. In a similar manner, Al-AsSi3 can be deposited using P / As, As / N, and P / N hybrids by forming corresponding intermediates using mixtures of As(SiH3)3, P(SiH3)3, and N(SiH3)3 for reaction with Al, and can also be deposited using As(SiH3)3 precursors. This work involves Al-PSi3 by introducing precursor mixtures of P(SiH3)3 and P(GeH3)3. 3x Ge 3(1-x) It can be extended to deposition.

[0032] Sims et al. (Chem. Mater. 2015, 27, 8, 3030-3039) described Al(BH4)3 formed by a low P CVD process using P(SiH3)3 and Al(BH4)3 precursors and grown on a Si-based solid phase. 1-x B x A hybrid of a group III material such as PSi3 (x = 0.04 ~ 0.06) is disclosed.

[0033] 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 a Si substrate using gas source MBE. When N(SiH3)3 is added to the reaction mixture under appropriate conditions, a novel hybrid material, Al(As 1-x N x )Si3 and Al(P 1-x N x ) y Si 5-2y is generated.

[0034] WO 2019066825 / US 20200168462 (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 corresponding hydrides and / or silylated chemical species including phosphine, arsine, stevin and bismuth, etc.

[0035] US7029995 (Todd et al.) discloses a method for forming an epitaxial film, wherein phosphorus, arsenic, and antimony are supplied in the form of precursors such as phosphine, trisilylphosphine, arsine, trisilylarzine, stibin, and silylstibin.

[0036] US9099423 (Weeks et al.) discloses a doped semiconductor film and processing, wherein the dopant includes phosphorus.

[0037] US6716751(Todd) contains (H3Si) 3-x Silicon alloys and doped silicon films formed by CVD and ion implantation processes using Si-containing precursors including MRx, (H3Si)3N, and (H3Si)4N2 are disclosed, wherein R is H or D, x = 0, 1 or 2, and M is selected from the group consisting of B, P, As and Sb.

[0038] US4910153 (Dickson) contains the chemical formula (MX3) n M'X 4-n A deposition precursor having the formula is disclosed, wherein M and M' are different Group 4A atoms, at least one of M and M' is silicon, X is hydrogen, a halogen or a mixture thereof, and n = 1 to 4 (including the end). The dopant has the formula (SiX3). m LX 3-m It has, where L is a group 5A atom selected from the group of 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 end point).

[0039] Chemical formula A(SiH3) 3-x (H or D) x Applications of compounds having [the following] are described, for example, in WO 2002065508 (specifically, when used in combination with a Si source that is a polysilane such as disilane or trisilane). This chemical choice makes it possible to deposit films at lower temperatures than the classical SiH4 / PH3 / AsH3 chemistry used in such processes, and thus enables the deposition of films with a dopant concentration higher than the solubility value of the dopant in silicon.

[0040] A method for synthesizing a compound containing a group V element is disclosed, and the method comprises the following steps:

[0041] A step of contacting A(SiR3)3 with one, two, or three types of halo(poly)silane(s) (series or mixture) (wherein the halo(poly)silane is X-Si a H 2a+1 ,X-Si b H 2b+1 and X-Si c H 2c+1 Selected from a group consisting of); and

[0042] Dehalosilylated A(SiR3)3 to form a Group V element-containing compound

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

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

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

[0046] Step of forming (through the following stepwise general reaction(s):

[0047] a). Step 1 reaction:

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

[0049] b). Step 2 reaction:

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

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

[0052] c). Step 3 reaction:

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

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

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

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

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

[0058] (Here,

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

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

[0061] m = 1 to 3 and;

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

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

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

[0065] R is C1 to C 10 , selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups). The disclosed method may include one or more of the following embodiments:

[0066] · Mode in which a solvent is added;

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

[0068] · An embodiment in which the ratio of solvent to A(SiR3)3 is 0 to 99 wt%;

[0069] · The alkane or aromatic solvent is an embodiment selected from pentane, hexane, heptane, benzene, toluene, xylene, chlorotrimethylsilane, or a mixture thereof;

[0070] · An embodiment in which the ratio of halo(poly)silane:A(SiR3)3 is in the range of 1:99 to 99:1;

[0071] · An embodiment in which the ratio of halo(poly)silane:A(SiR3)3 is in the range of 1:20 to 20:1;

[0072] · An embodiment in which the ratio of halo(poly)silane:A(SiR3)3 is in the range of 1:5 to 5:1;

[0073] · X is a mode in which Cl;

[0074] · Halo(poly)silane is a chloro(poly)silane in the form of a mode;

[0075] · Chloro(poly)silanes are Cl-Si a H 2a+1 , Cl-Si b H 2b+1 and / or Cl-Si a H 2a+1 And, where, a = 1 to 6; b = 1 to 6; c = 1 to 6; and a ≠ b ≠ c;

[0076] · Chloro(poly)silane is in the form of Cl-SiH3, Cl-Si2H5, or Cl-Si3H7;

[0077] · A mode where R is a methyl group (Me);

[0078] · A step of isolating the group V element-containing compound by separating the solvent and reaction product; and

[0079] An embodiment further comprising a step of purifying a compound containing a group V element;

[0080] · An embodiment in which the purity of the group V element-containing compound is > 90%;

[0081] · An embodiment in which the purity of the group V element-containing compound is > 95%;

[0082] · An embodiment in which the purity of the group V element-containing compound is > 98%;

[0083] · The present method is a batch process mode;

[0084] · An embodiment in which the reaction is maintained at a temperature in the range of -20℃ to 150℃;

[0085] · An embodiment in which the reaction is maintained at a temperature in the range of room temperature to 100°C;

[0086] · A group V element-containing compound in a form containing a trisilyl group;

[0087] · An embodiment in which the trisilyl group is -SiH(SiH3)2(i-trisilyl);

[0088] · An embodiment in which the trisilyl group is -SiH2-SiH2-SiH3(n-trisilyl);

[0089] · V족 원소-함유 화합물은 P(SiH3)3, P(SiR3)(SiH3)2, P(SiR3)2(SiH3), P(SiR3)(Si2H5)2, P(SiR3)2(Si2H5), P(Si2H5)3, P(SiR3)(Si3H7)2, P(SiR3)2(Si3H7), P(Si3H7)3, As(SiH3)3, As(SiR3)(SiH3)2, As(SiR3)2(SiH3), As(SiR3)(Si2H5)2, As(SiR3)2(Si2H5), As(Si2H5)3, As(SiR3)(Si3H7)2, As(SiR3)2(Si3H7), As(Si3H7)3, Sb(SiH3)3, Sb(SiR3)(SiH3)2, Sb(SiR3)2(SiH3), Sb(SiR3)(Si2H5)2, Sb(SiR3)2(Si2H5), Sb(Si2H5)3, Sb(SIR3)(Si3H7)2, Sb(SiR3)2(Si3H7), Sb(Si3H7) 3, P(SiR3)(SiH3)(Si2H5), P(SiR3)(SiH3)(Si3H7), P(SiH3)2(Si2H5), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7), P(Si2H5)(Si3H7)2, As(SiR3)(SiH3)(Si2H5), As(SiR3)(SiH3)(Si3H7), As(SiH3)2(Si2H5), As(SiH3)2(Si3H7), As(SiH3)(Si2H5)2, As(SiH3)(Si2H5)(Si3H7), As(SiH3)(Si3H7)2, As(Si2H5)2(Si3H7), As(Si2H5)(Si3H7)2, Sb(SiR3)(SiH3)(Si2H5), Sb(SiR3)(SiH3)(Si3H7), Sb(SiH3)2(Si2H5), Sb(SiH3)2(Si3H7), Sb(SiH3)(Si2H5)2, Sb(SiH3)(Si2H5)(Si3H7), Sb(SiH3)(Si3H7)2, Sb(Si2H5)2(Si3H7), 또는 Sb(Si2H5)(Si3H7)2로부터 선택되는 양태;

[0090] · R is a modality selected from Me, Et, nPr, iPr, tBu, nBu, iBu, or sBu;

[0091] · When R = Me, 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, As(SiH3)(Si2H5)(Si3H7), As(SiH3)(Si3H7)2, An embodiment selected from 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;

[0092] · Group V element-containing compounds are from the group consisting of P(SiH3)3, P(TMS)(SiH3)2, P(TMS)2(SiH3), P(TMS)(Si2H5)2, P(TMS)2(Si2H5), P(Si2H5)3, P(TMS)(Si3H7)2, P(TMS)2(Si3H7), P(Si3H7)3, P(TMS)(SiH3)(Si2H5), P(TMS)(SiH3)(Si3H7), P(SiH3)2(Si2H5), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7), and P(Si2H5)(Si3H7)2 Selected mode;

[0093] · Group V element-containing compounds are A(Si2H5)(SiR3)2, A(Si3H7)(SiR3)2, when n = 2 to 3, Selected from the group consisting of 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 to C 10 , selected from linear, branched or cyclic alkyl, alkenyl, and alkynyl groups; provided that if A = P, P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) are excluded; and

[0094] · For Group V element-containing compounds, when m = 3, A(Si a H 2a+1 )3, where, a = 1 to 6; A is a group V element selected from P, As, Sb or Bi; and R is C1 to C 10 An embodiment selected from linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups; provided that if A = As, a > 1; if A = P, P(Si2H5)3 is excluded; and if A = Sb, Sb(SiH3)3 is excluded.

[0095] A group V element-containing compound having the following chemical formula is also disclosed:

[0096] (SiR3) 3-m A(Si a H 2a+1 ) m ,

[0097] (SiR3) 3-n-p A(Si a H 2a+1 ) n (Si b H 2b+1 ) p or

[0098] A(Si a H 2a+1 )(Si b H 2b+1 )(Si c H 2c+1 )

[0099] (Here,

[0100] a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c;

[0101] m = 1 to 3 and;

[0102] n = 1 to 2, p = 1 to 2, and n + p = 2 to 3;

[0103] A = a group V element selected from As, P, Sb, and Bi;

[0104] R is C1 to C 10 , selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups;

[0105] Provided, 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 compound may include one or more of the following embodiments:

[0106] · An embodiment in which the purity of the group V element-containing compound is > 93%;

[0107] · An embodiment in which the purity of the group V element-containing compound is > 95%; and

[0108] · An embodiment in which the purity of a Group V element-containing compound is > 98%.

[0109] A method for forming a Si and group V element-containing film on a substrate is also disclosed, and the method

[0110] A step of exposing a substrate to the vapor of a film-forming composition containing Si and a group V element-containing precursor; and

[0111] The method includes the step of forming a Si and Group V element-containing film on a substrate by depositing at least a portion of a Si and Group V element-containing precursor on a substrate through a vapor deposition method.

[0112] Here, the Si and Group V element-containing precursors have the following general chemical formulas:

[0113] (SiR3) 3-m A(Si a H 2a+1 ) m ,

[0114] (SiR3) 3-n-p A(Si a H 2a+1 ) n (Si b H 2b+1 ) p or

[0115] A(Si a H 2a+1 )(Si b H 2b+1 )(Si c H 2c+1 )

[0116] (Here,

[0117] A is a group V element selected from P, As, Sb, or Bi;

[0118] a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c;

[0119] m = 1 to 3 and;

[0120] n = 1 to 2, p = 1 to 2, and n + p = 2 to 3;

[0121] R is C1 to C 10 , selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups;

[0122] However, 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 method may include one or more of the following embodiments:

[0123] · V족 원소-함유 전구체는 P(SiH3)3, P(SiR3)(SiH3)2, P(SiR3)2(SiH3), P(SiR3)(Si2H5)2, P(SiR3)2(Si2H5), P(Si2H5)3, P(SiR3)(Si3H7)2, P(SiR3)2(Si3H7), P(Si3H7)3, As(SiH3)3, As(SiR3)(SiH3)2, As(SiR3)2(SiH3), As(SiR3)(Si2H5)2, As(SiR3)2(Si2H5), As(Si2H5)3, As(SiR3)(Si3H7)2, As(SiR3)2(Si3H7), As(Si3H7)3, Sb(SiH3)3, Sb(SiR3)(SiH3)2, Sb(SiR3)2(SiH3), Sb(SiR3)(Si2H5)2, Sb(SiR3)2(Si2H5), Sb(Si2H5)3, Sb(SIR3)(Si3H7)2, Sb(SiR3)2(Si3H7), Sb(Si3H7) 3, P(SiR3)(SiH3)(Si2H5), P(SiR3)(SiH3)(Si3H7), P(SiH3)2(Si2H5), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7), P(Si2H5)(Si3H7)2, As(SiR3)(SiH3)(Si2H5), As(SiR3)(SiH3)(Si3H7), As(SiH3)2(Si2H5), As(SiH3)2(Si3H7), As(SiH3)(Si2H5)2, As(SiH3)(Si2H5)(Si3H7), As(SiH3)(Si3H7)2, As(Si2H5)2(Si3H7), As(Si2H5)(Si3H7)2, Sb(SiR3)(SiH3)(Si2H5), Sb(SiR3)(SiH3)(Si3H7), Sb(SiH3)2(Si2H5), Sb(SiH3)2(Si3H7), Sb(SiH3)(Si2H5)2, Sb(SiH3)(Si2H5)(Si3H7), Sb(SiH3)(Si3H7)2, Sb(Si2H5)2(Si3H7), 또는 Sb(Si2H5)(Si3H7)2로부터 선택되는 양태;

[0124] · R is a modality selected from Me, Et, nPr, iPr, tBu, nBu, iBu, or sBu;

[0125] · Si and Group V element-containing precursors 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(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)(Si3H7), As(SiH3)(Si3H7)2, As(Si2H5)2(Si3H7), As(Si2H5)(Si3H7)2, An embodiment selected from 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;

[0126] · A Si and group V element-containing precursor is an embodiment 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;

[0127] · A vapor deposition method comprises an embodiment including a CVD process, an ALD process, an epitaxy process, or a combination thereof;

[0128] · An embodiment in which the film-forming composition is activated by heating the substrate to a temperature in the range of 200°C to 1000°C, by plasma activating the Si and Group V element-containing precursors, or by a combination thereof;

[0129] · An embodiment further comprising the step of exposing the substrate to a co-reactant;

[0130] · Co-reactants in a plasma-activated mode;

[0131] · Co-reactants in a mode where plasma is not activated;

[0132] · An embodiment in which the co-reactant is an oxygen-containing gas selected from O2, O3, H2O, H2O2, NO, N2O, NO2, O radical, alcohol, silanol, amino alcohol, carboxylic acid, para-formaldehyde, or a combination thereof;

[0133] · A mode in which the co-reactant is O3;

[0134] · An embodiment in which 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, amine, trisilylamine, silazane, or a combination thereof;

[0135] · The co-reactant is H2;

[0136] · Co-reactant is N2;

[0137] · An embodiment in which 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, halosilane, phosphine, borane, or halide-containing gases;

[0138] · An embodiment in which the co-reactant is a diluent gas selected from Ar, He, N2, H2, or a combination thereof;

[0139] · An embodiment in which the Si and Group V element-containing film is a P-doped silicon-containing film;

[0140] · An embodiment further comprising the step of annealing a Si and group V element-containing layer through thermal annealing, furnace annealing, rapid thermal annealing, UV or e-beam curing, and / or plasma gas exposure;

[0141] · An embodiment in which the substrate is a powder; and

[0142] · An embodiment in which the powder comprises one or more of NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials.

[0143] A film-forming composition for depositing a film comprising a Si and a group V element-containing precursor having the following chemical formula is also disclosed:

[0144] (SiR3) 3-m A(Si a H 2a+1 ) m ,

[0145] (SiR3) 3-n-p A(Si a H 2a+1 ) n (Si b H 2b+1 ) p or

[0146] A(Si a H 2a+1 )(Si b H 2b+1 )(Si c H2c+1 )

[0147] (Here,

[0148] A is a group V element selected from P, As, Sb, or Bi;

[0149] a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c;

[0150] m = 1 to 3 and;

[0151] n = 1 to 2, p = 1 to 2, and n + p = 2 to 3;

[0152] R is C1 to C 10 , selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups;

[0153] (However, 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 comprises one or more of the following embodiments:

[0154] · V족 원소-함유 전구체는 P(SiH3)3, P(SiR3)(SiH3)2, P(SiR3)2(SiH3), P(SiR3)(Si2H5)2, P(SiR3)2(Si2H5), P(Si2H5)3, P(SiR3)(Si3H7)2, P(SiR3)2(Si3H7), P(Si3H7)3, As(SiH3)3, As(SiR3)(SiH3)2, As(SiR3)2(SiH3), As(SiR3)(Si2H5)2, As(SiR3)2(Si2H5), As(Si2H5)3, As(SiR3)(Si3H7)2, As(SiR3)2(Si3H7), As(Si3H7)3, Sb(SiH3)3, Sb(SiR3)(SiH3)2, Sb(SiR3)2(SiH3), Sb(SiR3)(Si2H5)2, Sb(SiR3)2(Si2H5), Sb(Si2H5)3, Sb(SIR3)(Si3H7)2, Sb(SiR3)2(Si3H7), Sb(Si3H7) 3, P(SiR3)(SiH3)(Si2H5), P(SiR3)(SiH3)(Si3H7), P(SiH3)2(Si2H5), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7), P(Si2H5)(Si3H7)2, As(SiR3)(SiH3)(Si2H5), As(SiR3)(SiH3)(Si3H7), As(SiH3)2(Si2H5), As(SiH3)2(Si3H7), As(SiH3)(Si2H5)2, As(SiH3)(Si2H5)(Si3H7), As(SiH3)(Si3H7)2, As(Si2H5)2(Si3H7), As(Si2H5)(Si3H7)2, Sb(SiR3)(SiH3)(Si2H5), Sb(SiR3)(SiH3)(Si3H7), Sb(SiH3)2(Si2H5), Sb(SiH3)2(Si3H7), Sb(SiH3)(Si2H5)2, Sb(SiH3)(Si2H5)(Si3H7), Sb(SiH3)(Si3H7)2, Sb(Si2H5)2(Si3H7), 또는 Sb(Si2H5)(Si3H7)2로부터 선택되는 양태;

[0155] · R is a modality selected from Me, Et, nPr, iPr, tBu, nBu, iBu, or sBu;

[0156] · Si and Group V element-containing precursors, when R = Me, 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(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)(Si3H7), As(SiH3)(Si3H7)2, As(Si2H5)2(Si3H7), As(Si2H5)(Si3H7)2, An embodiment selected from 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;

[0157] · An embodiment in which the purity of the Si and Group V element-containing precursor is > 93%;

[0158] · An embodiment in which the purity of the Si and Group V element-containing precursor is > 95%;

[0159] · An embodiment in which the purity of the Si and Group V element-containing precursor is > 93%.

[0160] A wet film-forming composition for spin coating of a film comprising a disclosed Si and Group V element-containing precursor of Formula I, II, or III having at least five Si atoms is also disclosed. The disclosed wet film-forming composition may comprise one or more of the following embodiments:

[0161] · An embodiment in which a Si and group V element-containing precursor of formula I, II, or III having the lowest volatility is selected to remain in the spun film during the annealing step and decompose in situ;

[0162] · An embodiment further comprising a co-reactant which is a polysilane or a polysilane mixture having five or more silicon atoms;

[0163] · Polysilane is a cyclopentasilan;

[0164] · Polysilane is a cyclohexasilane in the form of;

[0165] · An embodiment further comprising a solvent;

[0166] · An embodiment in which the spun film is an amorphous or polycrystalline Si film;

[0167] · An embodiment in which the spun film is an amorphous polycrystalline Si film;

[0168] · The spun film is an amorphous Si film;

[0169] · The spun film is a polycrystalline Si film;

[0170] A method for forming a group V element-doped epitaxial Si film on a substrate is also disclosed, and the method

[0171] A step of maintaining the substrate at a deposition temperature or a predetermined temperature near it;

[0172] A step of exposing a substrate to a mixture of vapor of a film-forming composition containing Si and a group V element-containing precursor and vapor of a co-reactant polysilane; and

[0173] The method includes the step of forming a group V element-doped epitaxial Si film on a substrate by depositing at least a portion of Si and a group V element-containing precursor on a substrate through a CVD process.

[0174] Here, the Si and Group V element-containing precursors have the following general chemical formulas:

[0175] (SiR3) 3-m A(Si a H 2a+1 ) m ,

[0176] (SiR3) 3-n-p A(Si a H 2a+1 ) n (Si b H 2b+1 ) p or

[0177] A(Si a H 2a+1 )(Si b H 2b+1 )(Si c H 2c+1 )

[0178] (Here,

[0179] A is a group V element selected from P, As, Sb, or Bi;

[0180] a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c;

[0181] m = 1 to 3 and;

[0182] n = 1 to 2, p = 1 to 2, and n + p = 2 to 3;

[0183] R is C1 to C 10 , selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups;

[0184] However, 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 method may include one or more of the following embodiments:

[0185] · An embodiment in which the mixture comprises a diluent gas selected from Ar, He, N2, H2, or a combination thereof;

[0186] · Co-reactant polysilane is a Germanic mode;

[0187] · An embodiment in which the predetermined temperature is in the range of 200℃ to 1000℃;

[0188] · An embodiment in which the deposition temperature is in the range of 200℃ to 1000℃;

[0189] · When A is P, the group V element-doped epitaxial Si film is a P-doped epitaxial Si film.

[0190] Notation and Naming

[0191] The following detailed description and claims use many abbreviations, symbols, and terms generally well known in the art. On the other hand, definitions are typically provided with the first example of each acronym, such as stainless steel (SS). Specific abbreviations, symbols, and terms are used throughout the following description and claims and include the following:

[0192] The following detailed description and claims use many abbreviations, symbols, and terms generally well known in the art.

[0193] As used herein, the singular form means one or more.

[0194] As used herein, "about, around" or "approximately" in the text or claims means ±10% of the stated value.

[0195] As used herein, "room temperature" in the text or claims means approximately 20°C to approximately 25°C.

[0196] As used herein, "atmospheric pressure" in the text or claims means approximately 1 atm.

[0197] 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 the manufacture of semiconductors, photovoltaics, flat panel or LCD-TFT devices. The substrate may also have one or more layers of different materials already deposited on the substrate from a previous manufacturing step. For example, the wafer may comprise 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. Additionally, the substrate may be planar or patterned. The substrate may be a patterned organic photoresist film. The substrate may comprise 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 as used herein, the terms “film” or “layer” refer to a portion of material of a certain thickness placed on or diffused over a surface, and that said surface may be a trench or a line. Throughout this specification and claims, a wafer and any associated layer thereon are referred to as a substrate.

[0198] The term "wafer" or "patterned wafer" refers to a wafer having a stack of films on a substrate, wherein at least the topmost film has topographic features generated in the pre-deposition steps of an indium-containing film.

[0199] The term "aspect ratio" refers to the ratio of the height of a trench (or opening) to the width (or diameter) of a trench.

[0200] 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 related to a layer, and that a layer may refer to a film. Furthermore, those skilled in the art will recognize that the terms “film” or “layer” as used herein refer to a portion of material of a certain thickness placed on or diffused over a surface, and that said surface may range from large enough to be an entire wafer to small enough to be a trench or a line.

[0201] It should be noted that in this document, the terms "opening," "via," "hole," and "trench" may be used interchangeably to refer to an opening formed in a semiconductor structure.

[0202] 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, wherein the gate structure is stacked in a vertical direction.

[0203] It is noted herein that the terms "deposition temperature" and "substrate temperature" may be used interchangeably. It is understood that the substrate temperature may correspond to or be related to the deposition temperature, and that the deposition temperature may refer to the substrate temperature.

[0204] It is noted herein that the terms "precursor," "deposited compound," and "deposited 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 related to the deposited compound or deposited gas, and that the deposited compound or deposited gas may refer to the precursor.

[0205] Standard abbreviations for elements from the periodic table are used herein. It should be understood that an element may be referred to by its abbreviation (for example, Si refers to silicon, N refers to nitrogen, O refers to oxygen, C refers to carbon, H refers to hydrogen, and Hal refers to the halogens F, Cl, Br, and I).

[0206] A unique CAS registration number (i.e., "CAS") assigned by the Chemical Abstract Service is provided to identify a specific disclosed molecule.

[0207] As used herein, the term "hydrocarbon" refers to a saturated or unsaturated functional group containing only carbon and hydrogen atoms.

[0208] It should be noted that silicon-containing films, such as SiN and SiO, are listed throughout this specification and claims without referring to their appropriate stoichiometry. Silicon-containing films are layers of pure silicon (Si), such as crystalline Si, polysilicon (p-Si or polycrystalline Si), or amorphous silicon; silicon nitride (Si k N l ) layer; or silicon oxide (Si n O m It may include a ) layer; or a mixture thereof, wherein k, l, m, and n are in the range of 0.1 to 6 (including the endpoint). Preferably, silicon nitride is Si k N l And, where k and l are each in the range of 0.5 to 1.5. More preferably, silicon nitride is Si3N4. In the following description, SiN refers to Si k N l It can be used to indicate a containing layer. Preferably, silicon oxide is Si n O mAnd, 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, silicon oxide is SiO2. In the following description, SiO is Si n O m It can be used to indicate a containing layer. The silicon-containing film may also be a silicon oxide-based dielectric material, such as an organic or silicon oxide-based low-k dielectric material, such as Black Diamond II or III material having the chemical formula SiOCH by Applied Materials, Inc. The silicon-containing film is also Si a O b N c It may include, where a, b, and c are in the range of 0.1 to 6. The silicon-containing film may also include dopants from groups III, IV, V and VI, such as B, C, P, As and / or Ge.

[0209] It should be noted that deposited films or layers, such as silicon oxide or silicon nitride, may be listed throughout this specification and claims without reference to appropriate stoichiometry (i.e., SiO, SiO2, Si3N4). Such layers include pure (Si) layers, carbides (Si o C p ) layer, nitride (Si k N l ) layer, oxide (Si n O m It may include a ) layer, or a mixture thereof, where k, l, m, n, o, and p are comprehensively in the range of 1 to 6. For example, silicon oxide is Si n O mAnd, 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 or silicon oxide-based low-k dielectric material, such as Black Diamond II or III material by Applied Materials, Inc. Alternatively, any mentioned silicon-containing layer may be pure silicon. Any silicon-containing layer may also include dopants such as B, C, P, As and / or Ge.

[0210] 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, iso-butyl, 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 iso-butyl group; the abbreviation "Ph" refers to a phenyl group; the abbreviation "Am" refers to any amyl group (iso-amyl, 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, mesithyl, etc.); and TMS refers to a trimethylsilyl-SiMe3 group.

[0211] A range may be expressed herein approximately from one specific value and / or approximately from another specific value. When such a range is expressed, it will be understood that other embodiments, together with all combinations within such a range, are from one particular value and / or another particular value. Any and all ranges listed herein include their endpoints regardless of whether the term “inclusively” is used (i.e., “x = 1 to 4” or “x is in the range of 1 to 4” includes “x = 1,” “x = 4,” and “x = any number in between”).

[0212] References to “one embodiment” or “embodiment” herein mean that a specific feature, structure, or characteristic described in relation to an embodiment may be included in at least one embodiment of the present invention. Appearances of the phrase “in one embodiment” in various places within this specification do not all refer to the same embodiment, nor are separate or alternative embodiments necessarily mutually exclusive from other embodiments. The same applies to the term “embodiment.”

[0213] As used in this application, the word “exemplary” is used to mean that it functions as an example, case, or illustration. Any embodiment or design described herein as “exemplary” is not to be interpreted as being more desirable or advantageous than any other embodiment or design. Rather, the use of the word “exemplary” is intended to provide the concept in a concrete manner.

[0214] Additionally, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless otherwise specified or is not evident from the context, "X uses A or B" is intended to mean any of the natural inclusive permutations. In other words, if X uses A; if X uses B; or if X uses both A and B, "X uses A or B" is satisfied in any of these cases. Furthermore, the singular forms (“a” and “an”) used in this application and the appended claims should generally be interpreted to mean "one or more" unless otherwise specified or the context clearly indicates a singular form. Brief explanation of the drawing

[0215] The above and various other aspects, features, and advantages of the present invention, as well as the invention itself, can be more fully understood by referring to the following detailed description of the invention in conjunction with the drawings. The drawings are provided for illustrative purposes only and are not intended to limit the invention. Fig. 1 is a GC chromatogram of the reaction mixture of P(TMS)3+7 MCTS (monochlorotrisilane, i.e., Si3H7Cl) in hexane at 68°C for 24 hours (Example 2). Fig. 2 is a GC chromatogram of the reaction mixture of P(TMS)3 + 3 MCS (monochlorosilane, i.e., SiH3Cl) at 90°C for 44 hours (Example 4). Fig. 3 is the GC chromatogram of the reaction mixture of As(TMS)3+6 MCTS at 60°C for 24 hours (Example 5). Fig. 4 is the GC chromatogram of the reaction mixture of Sb(TMS)3 + 10 MCS at 60°C for 24 hours (Example 8). Specific details for implementing the invention

[0216] A Group V element-containing film-forming composition comprising a Group V element-containing precursor containing an inorganic silyl and a polysilyl, a method for synthesizing the same, and a method for depositing a Group V element-containing film using the same are disclosed.

[0217] The disclosed Group V element-containing precursor has the following general chemical formula:

[0218] [Chemical Formula I]

[0219] (SiR3) 3-m A(Si a H 2a+1 ) m

[0220] [Chemical Formula II]

[0221] (SiR3) 3-n-p A(Si a H 2a+1 ) n (Si b H 2b+1 ) p

[0222] [Chemical Formula III]

[0223] A(Si a H 2a+1 )(Si b H 2b+1 )(Si c H 2c+1 )

[0224] (Here, A is a group V element selected from P, As, Sb or Bi;

[0225] a = 1 to 6; b = 1 to 6; c = 1 to 6; a ≠ b ≠ c;

[0226] m = 1 to 3 and;

[0227] n = 1 to 2, p = 1 to 2, and n + p = 2 to 3;

[0228] R is C1 to C 10 , selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups;

[0229] However, 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).

[0230] The disclosed group V element-containing precursor contains a trisilyl group that may be -SiH(SiH3)2(i-trisilyl) or -SiH2-SiH2-SiH3(n-trisilyl).

[0231] An exemplary disclosed precursor is P(SiH3)3, P(SiR3)(SiH3)2, P(SiR3)2(SiH3), P(SiR3)(Si2H5)2, P(SiR3)2(Si2H5), P(Si2H5)3, P(SiR3)(Si3H7)2, P(SiR3)2(Si3H7), P(Si3H7)3, As(SiH3)3, As(SiR3)(SiH3)2, As(SiR3)2(SiH3), As(SiR3)(Si2H5)2, As(SiR3)2(Si2H5), As(Si2H5)3, As(SiR3)(Si3H7)2, As(SiR3)2(Si3H7), As(Si3H7)3, Sb(SiH3)3, Sb(SiR3)(SiH3)2, Sb(SiR3)2(SiH3), Sb(SiR3)(Si2H5)2, Sb(SiR3)2(Si2H5), Sb(Si2H5)3, Sb(SiR3)(Si3H7)2, Sb(SiR3)2(Si3H7), Sb(Si3H7) 3,P(SiR3)(SiH3)(Si2H5), P(SiR3)(SiH3)(Si3H7), P(SiH3)2(Si2H5), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7), P(Si2H5)(Si3H7)2, As(SiR3)(SiH3)(Si2H5), As(SiR3)(SiH3)(Si3H7), As(SiH3)2(Si2H5), As(SiH3)2(Si3H7), As(SiH3)(Si2H5)2, As(SiH3)(Si2H5)(Si3H7), As(SiH3)(Si3H7)2, Includes 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.

[0232] Preferably, when R is a methyl group, -CH3, the disclosed Group V element-containing precursor is A (Si a H 2a+1 ) m (Si(CH3)3) 3-m , or A(Si n H 2n+1 ) m (TMS) 3-mAnd, where, a = 1 to 6; m = 1 to 3; A is a group V element selected from P, As, Sb or Bi; provided that if A = As, a > 1; if A = P, P(SiH3)2(TMS) is excluded; and if A = Sb, Sb(SiH3)3 is excluded. When R = Me, the exemplary disclosed precursors 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, As(SiH3)(Si2H5)(Si3H7), As(SiH3)(Si3H7)2, It includes 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), and Sb(Si2H5)(Si3H7)2.

[0233] Preferably, when n = 2 to 3, the disclosed group V element-containing precursor is A(Si2H5)(SiR3)2, A(Si3H7)(SiR3)2, Selected from the group consisting of 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 to C 10 , selected from linear, branched or cyclic alkyl, alkenyl, and alkynyl groups; provided that if A = P, P(SiH3)2(Si2H5), P(SiH3)(Si2H5)2, P(Si2H5)3, and P(SiH3)2(TMS) are excluded.

[0234] Preferably, when m = 3, the disclosed Group V element-containing precursor is A(Si a H 2a+1)3, where, a = 1 to 6; A is a group V element selected from P, As, Sb or Bi; and R is C1 to C 10 , selected from linear, branched or cyclic alkyl, alkenyl, or alkynyl groups; provided that if A = As, n > 1; if A = P, P(Si2H5)3 is excluded; and if A = Sb, Sb(SiH3)3 is excluded.

[0235] The disclosed Group V element-containing precursor may be P(SiH3)3, P(TMS)(SiH3)2, P(TMS)2(SiH3), P(TMS)(Si2H5)2, P(TMS)2(Si2H5), P(Si2H5)3, P(TMS)(Si3H7)2, P(TMS)2(Si3H7), P(Si3H7)3, P(TMS)(SiH3)(Si2H5), P(TMS)(SiH3)(Si3H7), P(SiH3)2(Si2H5), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7), or P(Si2H5)(Si3H7)2.

[0236] A disclosed synthesis method for synthesizing a disclosed Group V element-containing precursor represented by chemical formulas I to III is a halosilyl or halopolysilyl compound (X-Si) according to the following general reaction scheme. n H 2n+1 Includes a dehalosilylation (DXS) pathway between ) and a tris(trialkylsilyl) derivative of A (A = As, P, Sb or Bi), A(SiR3)3:

[0237] [Reaction Equation IV]

[0238] A(SiR3)3+ m X-Si a H 2a+1 → A(Si a H 2a+1 ) m (SiR3) 3-m + m X-SiR3

[0239] (Here, a = 1 to 6 and;

[0240] m = 1 to 3, preferably m = 3;

[0241] A = As, P, Sb, Bi and;

[0242] X = Cl, Br, I and;

[0243] R is C1 to C 10 , selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups).

[0244] The disclosed synthesis method involves A(SiR3)3 with a halo(poly)silane (X-Si a H 2a+1 The method includes a step of contacting with ) (optional addition of a solvent), wherein the ratio of halo(poly)silane to A(SiR3)3 is in the range of 1:100 equivalents to 100:1 equivalents, preferably 1:20 equivalents to 20:1 equivalents, and preferably the halo(poly)silane is chloro(poly)silane. The solvent is the reactant A(SiR3)3 and the halo(poly)silane (X-Si a H 2a+1) is selected from an alkane or aromatic solvent that is inert to both, such as pentane, hexane, heptane, benzene, toluene, xylene, etc., or a haloalkylsilane, or a mixture thereof, and 0 to 99 weight percent corresponds to a reactant or starting material, such as A(SiR3)3. The optimal ratio of halo(poly)silane to A(SiR3)3 can be optimized to reach the target precursor with the highest yield. In reaction (VI), when a = 1 or 2, monochlorosilane (MCS, ClSiH3) or monochlorodisilane (MCDS, ClSiH2SiH3) can be added using a leak-proof manifold by direct liquid addition or by condensation of clean vapors (in a clean state or in a solvent). Then, the mixture of reactants can be stirred for a certain period of time, typically 1 to 168 hours, to form a reaction mixture. Subsequently, the product may be separated from the reaction mixture by the removal of the solvent and / or fractional distillation or by other suitable means known in the art. The isolated product may then be purified by distillation, for example, either in batch or continuous manner, to reach a desired product purity.

[0245] 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 room temperature to 100°C. The synthesis time is 1 to 168 hours, preferably 12 to 96 hours, more preferably 24 to 48 hours, depending on reaction conditions such as the reaction temperature.

[0246] Alternatively, the disclosed synthesis method can be carried out stepwise, and silyl groups of various sizes can be substituted sequentially, such as in a two-step or three-step reaction.

[0247] The initiated two-step reaction between a halosilyl or halopolysilyl compound and a tris(trialkylsilyl) derivative of A has the following general reaction scheme:

[0248] [Reaction Equation V]

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

[0250] [Reaction Equation VI]

[0251] (SiR3) 3-n A(Si a H 2a+1 ) n + p X-(Si b H 2b+1 ) → A(Si a H 2a+1 ) 3-n-p (Si b H 2b+1 ) p + p X-SiR3

[0252] (Here, a = 1 to 6 and b = 1 to 6;

[0253] n = 1 to 2, p = 1 to 2, and n + p = 2 to 3;

[0254] A = As, P, Sb, Bi and;

[0255] X = Cl, Br, I and;

[0256] R is C1 to C 10 , selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups).

[0257] The disclosed three-step reaction with a halosilyl or halopolysilyl and a tris(trialkylsilyl) derivative of A has the following general reaction scheme:

[0258] [Reaction Equation VII]

[0259] A(SiR3)3+ X-Si a H2a+1 → (SiR3)2A(Si a H 2a+1 ) + X-SiR3

[0260] [Reaction Equation VIII]

[0261] (SiR3)2A(Si a H 2a+1 ) + b H 2b+1 → (SiR3)A(Si a H 2a+1 )(Si b H 2b+1 ) + X-SiR3

[0262] [Reaction Equation IX]

[0263] (SiR3)A(Si a H 2a+1 )(Si b H 2b+1 ) + b H 2b+1 → A(Si a H 2a+1 )(Si b H 2b+1 )(Si c H 2c+1 ) + X-SiR3

[0264] (where, a = 1 to 6, b = 1 to 6, c = 1 to 6;

[0265] A = As, P, Sb, Bi and;

[0266] X = Cl, Br, I and;

[0267] R is C1 to C 10 , selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups).

[0268] Alternatively, the disclosed synthesis method can be carried out as a mixture or a one-pot, and silyl groups of various sizes can be substituted in a mixture in which all starting materials are mixed together.

[0269] The disclosed mixing reaction with a halosilyl or halopolysilyl and a tris(trialkylsilyl) derivative of A has the following general reaction scheme:

[0270] [Reaction Equation X]

[0271] A(SiR3)3+ x X-Si a H 2a+1 + y X-Si b H 2b+1 + z X-Si c H 2c+1 → A(Si a H 2a+1 ) x (Si b H 2b+1 ) y (Si c H 2c+1 ) z (SiR3) (3-x-y-z) + (x + y + z) X-SiR3

[0272] (where, a = 1 to 6, b = 1 to 6, c = 1 to 6;

[0273] x = 0 to 3, y = 0 to 3, z = 0 to 3, x + y + z = 1 to 3;

[0274] A = As, P, Sb, Bi and;

[0275] X = Cl, Br, I and;

[0276] R is C1 to C 10 , selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups).

[0277] In one embodiment, the disclosed synthesis method for synthesizing the disclosed Group V element-containing precursors exemplified in reaction schemes IV to X comprises 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 to C 10It is a dechlorosilylation (DCS) pathway between linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups.

[0278] The disclosed synthesis reaction can be carried out in batch mode. In this case, A(SiR3)3 may be added preferentially to a halo(poly)silane (e.g., chloro(poly)silane), and vice versa. If only partial substitution of the -SiR3 group on A is desired, it is preferable to add the halo(poly)silane preferentially to A(SiR3)3.

[0279] The disclosed synthesis reaction can be carried out in a continuous mode, where each reactant stream is fed and reacted continuously. A continuous mixing system may be used to facilitate contact with the reactants. The reaction may not result in any solid by-products, but in some cases, a filtration step may be added after synthesis to remove potential solid by-products. Volatile by-product(s) of the reaction can be continuously removed to allow the reaction to proceed toward completion or multi-stage conversion. This is a unique advantage of the disclosed synthesis method, which produces few or no solid by-product(s). It is understood that replacing the chloro(poly)silane reactant with bromo(poly)silane is not a significant deviation. Chlorinated silanes are more convenient for reasons of availability.

[0280] The disclosed synthesis method has the following unique advantages.

[0281] · Easily available starting materials: Conventional synthesis methods use reactants such as KPH2 and P(SnMe3)3 that are not readily available for purchase or require new manufacturing. In contrast, the disclosed synthesis method uses P(TMS)3, As(TMS)3, or Sb(TMS)3 as starting materials, which are available in large quantities and in high purity.

[0282] · Chlorosilanes are also much more readily available than their Br counterparts. SiH3Cl (MCS) is available as a commercial product. For example, Si2H5Cl (MCDS) and Si3H7Cl (MCTS) can be synthesized according to the literature [Cradock et al., J. Chem. Soc. Dalton Trans., 1975, 1624-1628].

[0283] · The disclosed synthesis method may be a one-step synthesis when only one type of polysilyl group is introduced. Most existing synthesis methods are multi-step reactions, in which mono- or di-silylphosphine, arsine, etc., such as SiH3PH2, Si2H5PH2, and LiAlH[P(SiH3)2]3 must be prepared in the first step(s) and subsequently isolated. In contrast, the disclosed synthesis method is a one-step and one-reactor process, and isolation of byproducts during synthesis is not necessarily required.

[0284] · The disclosed synthesis method has mild reaction conditions. Due to the instability of the starting materials, most conventional synthesis methods require the reaction to be carried out at low temperatures while appropriately controlling the rate of reactant addition and / or the rate of mixture thawing. In contrast, the disclosed synthesis method is carried out at ambient temperatures or slightly elevated temperatures, such as temperatures in the range of room temperature to 100°C.

[0285] · The disclosed synthesis method has fewer side reactions and a higher yield. The disclosed DHS route provides a relatively high yield as a result of fewer side reactions, which facilitates subsequent isolation and purification processes.

[0286] · The disclosed synthesis method has little to no salt formation, which is known to promote the degradation of similar molecules, such as its N-type analogs having a trisilylamine (TSA) backbone.

[0287] The disclosed group V element-containing film-forming precursor synthesized by the disclosed synthesis method can be used for vapor deposition of a Si-containing film having a group V element dopant on silicon through CVD, PECVD, ALD, PEALD, fluid CVD, HW-CVD, epitaxy, etc.

[0288] P and As compounds, particularly 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 on each silyl moiety, and y = 2x + 1) can be conveniently used as a dopant in silicon. In some applications, for example, to reduce contact resistance in semiconductor devices, it is very necessary to dope beyond the solubility limit of the dopant in silicon. Polysilanes and trisilanes can deposit silicon (e.g., amorphous or crystalline silicon) at a faster rate than silanes at temperatures lower than approximately 450°C. The disclosed Group V element-containing precursor having polysilyl ligands instead of silyl ligands will also result in deposition at lower temperatures and promote the inclusion of dopants.

[0289] The disclosed Group V element-containing precursor is provided in a high-purity container typically made of stainless steel, carbon steel, or aluminum, which has been previously dried to a residual H2O of less than 100 ppb and optionally passivated to limit the degradation of said precursor over time. The passivation process generally involves exposing the high-purity container to a silylating agent (which may be the target precursor itself, or a silane or polysilane).

[0290] The disclosed group V element-containing precursor preferably has 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 approximately 99.999% w / w or 99.0% w / w to 100.0% w / w), wherein metal impurities are in the ppb range and O-containing impurities are in the ppm to sub-ppm range, which is 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 disclosed Group V element-containing precursor can be purified by recrystallization, sublimation, distillation, and / or by passing the gaseous liquid through a suitable adsorbent such as a molecular sieve.

[0291] The disclosed Group V element-containing precursor may be supplied in pure form, as a blend with suitable solvents such as ethylbenzene, xylene, mesitylene, decalin, decane, dodecane, or in the form of polysilane or haloalkylsilane. The disclosed precursor may be present in the solvent at various concentrations.

[0292] The vapor of the disclosed Group V element-containing precursor can be delivered in a pure state into a process chamber in the absence of a carrier gas at a vessel temperature in the range of 0°C to approximately 150°C, where the vapor pressure of the precursor is typically > 50 torr, preferably > 300 torr.

[0293] In the case of the disclosed Group V element-containing precursor having a low vapor pressure, the vapor of the disclosed Group V element-containing precursor is supplied to a process chamber along with a carrier gas from a bubbler, a vapor extraction system, or a direct liquid injection system. The carrier gas may include, but is not limited to, Ar, He, N2, H2, and combinations thereof. Bubbling into the carrier gas may also remove any dissolved oxygen present in the precursor. Subsequently, the carrier gas and the precursor are introduced into the processing chamber as vapor. The process chamber is generally maintained at a pressure below atmospheric pressure, preferably in the range of 0.01 to 500 torr, more preferably in the range of 1 to 100 torr.

[0294] If necessary, the container containing the disclosed Group V element-containing precursor may be heated or cooled to a temperature that allows the precursor to have a sufficient and appropriate vapor pressure. The container may be maintained, for example, at a temperature in the range of approximately 0°C to approximately 200°C. Those skilled in the art recognize that the temperature of the container may be adjusted in a known manner to control the amount of vaporized precursor.

[0295] The processing chamber may be any enclosure chamber within the device where the deposition method is performed, such as a parallel-plate reactor, a low-temperature-wall reactor, a high-temperature-wall reactor, a single-wafer reactor, a multi-wafer reactor, or other types of deposition systems, without limitation, under suitable conditions that cause the precursor to react to form a deposited film. Those skilled in the art will recognize that any of these processing chambers may be used in either an ALD or CVD deposition process.

[0296] A processing chamber accommodates one or more substrates on which a film is to be deposited. A substrate is generally defined as the material on which the process is performed. The substrate may be any suitable substrate used in the manufacture of semiconductors, photovoltaic cells, flat panel, or LCD-TFT devices. Examples of suitable substrates include wafers such as silicon wafers, silica wafers, glass wafers, and GaAs wafers. The wafer may have one or more layers of different materials deposited on the wafer from a previous manufacturing step. For example, the wafer may include a dielectric layer or a 3D NAND stack. Additionally, the wafer may include a silicon layer (crystalline, amorphous, porous, etc.), a silicon oxide layer, a silicon nitride layer, a silicon oxynitride layer, a carbon-doped silicon oxide (SiCOH) layer, a metal, a metal oxide layer, a metal nitride layer (Ti, Ru, Ta, etc.), and combinations thereof. Furthermore, the wafer may include a copper layer and a precious metal layer (e.g., platinum, palladium, rhodium, gold). The wafer may include a barrier layer such as manganese, manganese oxide, etc. A plastic layer may also be used. The layer may be planar or patterned. The disclosed vapor deposition process may deposit the layer directly onto a wafer or directly onto one or more layers on top of the wafer when the patterned layer is formed on a substrate. The patterned layer may be an alternating layer of two specific layers, such as SiO and SiN used in 3D NAND.

[0297] The end applications of the substrates are not limited to the present invention, but the technology may be particularly advantageous for the following types of substrates: 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.

[0298] The temperature and pressure within the processing chamber are maintained under conditions suitable for vapor deposition, such as ALD and CVD. In other words, after a vaporized, initiated precursor containing a Group V element is introduced into the chamber, the conditions within the chamber cause at least a portion of the precursor to be deposited on the substrate to form a layer. For example, the pressure within the reactor or the deposition pressure is about 10 as required by the deposition parameters. -3 torr to about 500 torr, preferably about 10 -2 It can be maintained at torr to 500 torr, more preferably at about 1 torr to 100 torr. Likewise, the temperature in the reactor or the deposition temperature can be maintained at room temperature to about 1000°C, preferably at 200°C to about 800°C. Those skilled in the art will know that "at least a portion of the precursor is deposited" means that some or all of the precursor reacts with the substrate or adheres to the substrate.

[0299] The temperature for achieving optimal film growth can be controlled by controlling the temperature of the substrate holder. Devices used to heat the substrate are known in the art. The substrate is heated to a temperature sufficient to obtain a desired film having a desired physical state and composition at a sufficient growth rate. Non-limiting exemplary temperature ranges in 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 be in the range of 200°C to approximately 800°C.

[0300] Alternatively, the substrate may be heated to a temperature sufficient to obtain a desired deposited film of a desired physical state and composition at a sufficient growth rate. The substrate(s) temperature may be maintained in a range of approximately 200°C to 1000°C, preferably 200°C to 800°C, more preferably 250°C to 600°C.

[0301] More specifically, in addition to the disclosed Group V element-containing precursors, other precursors or co-reactants such as, but not limited to, the following may also be introduced into the processing chamber: H2, silanes, polysilanes (Si2 to Si6, linear, branched, or cyclic (in the case of Si5 and Si6)), alkylsilanes, such as monomethylsilane, halosilanes (Cl-SiH3, Cl2SiH2, I2-SiH2, Cl3SiH , SiCl4, etc.) and polyhalopolysilanes (Si2Cl6, Si2HCl5, Cl-Si2H5, etc.), germanes, chlorogermanes, digermanes, polygermanes, halogermanes, phosphines, boranes, e.g., B2H6, diborane, halide-containing gases (HCl, Cl2, HBr, etc.); N-containing gases (NH3, N2, N2 / H2, 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).

[0302] Additionally, a diluent gas may be added to the process and is selected from Ar, He, N2, H2, or a combination thereof.

[0303] Additionally, the co-reactant may be treated with plasma to decompose the aforementioned precursor or reactant into its radical form, and when treated with plasma, at least one of H2, N2, and O2 or an inert gas (He, Ar, Kr, Xe) may be used depending on the target film composition. 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 at a power range of about 10 W to about 1000 W, preferably about 50 W to about 500 W. The plasma may be generated and present within the reactor itself. Alternatively, the plasma may generally be located at a location away from the reactor, for example, in a remotely located plasma system. Those skilled in the art will recognize methods and apparatus suitable for such plasma treatment.

[0304] For example, the co-reactant can be introduced into a direct plasma reactor that generates plasma in a reaction chamber to produce a plasma-treated reactant in a processing chamber. An exemplary direct plasma reactor includes the Titan™ PECVD System manufactured by Trion Technologies. The co-reactant can be introduced and maintained in the processing chamber prior to plasma processing. Alternatively, plasma processing can occur 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 the showerhead may be electrodes powered depending on whether cation collisions occur. The output typically applied to the in situ plasma generator is approximately 30 W to approximately 1000 W. Preferably, in the disclosed method, an output of approximately 30 W to approximately 600 W is used. More preferably, the output is in the range of approximately 100 W to approximately 500 W. Since the dissociation of co-reactants using in-situ plasma is typically less than that achieved using a remote plasma source for the same power input, it is not as efficient as a remote plasma system for reactant dissociation, and a remote plasma system may be advantageous for depositing films on substrates that are easily damaged by plasma.

[0305] Alternatively, plasma-treated co-reactants can be generated outside the processing chamber, for example, with a remote plasma to treat the co-reactants before they enter the processing chamber.

[0306] The vapor deposition process can be selective or non-selective for specific surfaces.

[0307] The vapor deposition process can be thermally driven or enhanced by plasma activation, photoactivation, microwave activation, or other suitable means to activate the molecular and growth processes.

[0308] The disclosed Group V element-containing film-forming composition may 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-ray CVD (HWCVD, also known as cat-CVD; where the hot-ray acts as the energy source for the deposition process), radicals-incorporated CVD, and combinations thereof. Exemplary ALD methods include thermal ALD, plasma-enhanced ALD (PEALD), space ALD, hot-ray ALD (HWALD), radicals-incorporated ALD, and combinations thereof. The deposition method is preferably a hot wall or cold wall thermal CVD capable of depositing an epitaxial film or an amorphous film containing Si and a dopant element of the claimed compound, and optionally Ge and / or other co-dopants.

[0309] In the ALD process, the ALD conditions within the chamber cause the disclosed Group V element-containing film-forming composition, which is adsorbed or chemically adsorbed on the substrate surface, to react and form a film on the substrate. In some embodiments, the applicant believes that plasma treating the co-reactant can provide the co-reactant with the energy required to react with the disclosed Group V element-containing film-forming composition (PEALD). The co-reactant may be plasma treated before or after being introduced into the chamber.

[0310] Group V element-containing precursors and co-reactants may be introduced sequentially into the reactor (ALD). The processing chamber may be purged with an inert gas between the introduction of each of the Group V element-containing precursor, any additional precursor, and co-reactant. Another example is to introduce the co-reactants sequentially while activating the co-reactants with plasma, and to introduce the Group V element-containing precursors by pulse, provided that the Group V element-containing precursors and the unactivated co-reactants do not substantially react under chamber temperature and pressure conditions (CW PEALD).

[0311] Each pulse of the disclosed Group V element-containing precursor may be sustained for a period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 second to about 80 seconds, or alternatively from about 5 seconds to about 30 seconds. The co-reactant may also be pulsed into the reactor, and in such an embodiment, each pulse may be sustained for a period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 second to about 30 seconds, or alternatively from about 2 seconds to about 20 seconds. In another alternative, the vaporized Group V element-containing precursor and the co-reactant may be sprayed simultaneously from different sectors of a showerhead without mixing, where a susceptor supporting multiple wafers is rotated below the showerhead (space ALD).

[0312] Depending on specific process parameters, deposition can occur for varying lengths of time. Generally, deposition can be continued as long as needed to produce a film with the required properties. Typical film thicknesses can vary from a few angstroms to hundreds of micrometers, and typically from 2 nm to 100 nm, depending on the specific deposition process. The deposition process can also be performed multiple times as needed to obtain the desired film.

[0313] The disclosed Group V element-containing precursor and co-reactant may be introduced into the reactor simultaneously (CVD), sequentially (ALD), or in different combinations thereof. The reactor may be purged with an inert gas (e.g., N2, Ar, Kr, Xe) between the introduction of the Group V element-containing precursor and the introduction of the co-reactant. Alternatively, the co-reactant and the Group V element-containing precursor may be mixed together to form a co-reactant / compound mixture, which is then introduced into the reactor in the form of a mixture (CVD, thermal CVD, or epitaxy). Another example involves introducing the co-reactant sequentially and introducing the disclosed Group V element-containing precursor by pulse (pulse CVD).

[0314] The desired film thickness may be in the range of molecular monolayer to 10 μm, preferably 1 nm to 500 nm.

[0315] Depending on the co-reactant, the deposition process may include elements other than those present in the claimed precursor, such as Ge, Ga, C, B, Sn, Al, N, O, S, Se, Te, In, Zn, Cd, and Hg.

[0316] A film deposited using the disclosed deposition method may be a p-doped Si and a film containing a group V element.

[0317] The film deposited using the disclosed deposition method may be a silicon layer doped with a group V element, such as a P-doped silicon layer.

[0318] The disclosed Group V element-containing film-forming composition can be used for liquid film deposition of Si-containing films, including but not limited to spin coating, dip coating, or spray coating. In this case, a formulation containing the disclosed compound is coated onto a substrate and then annealed to produce a thin film.

[0319] The disclosed Group V element-containing film-forming compositions are particularly useful as doping components for formulations aimed at producing amorphous and polycrystalline Si films. Such formulations typically comprise a solvent and a mixture of large polysilanes or polysilanes (such as cyclopentasilan, cyclohexasilane, etc.) having five or more silicon atoms. After coating a substrate with said formulation, the film is processed to produce a silicon film. For such spin coating applications, the selected precursor must have low volatility so that it remains in the spun film during the annealing step and decomposes in situ. Precursors of a family having at least five Si atoms are typically suitable for such applications.

[0320] Treatment typically involves heating (200 to 1000°C) and / or light / UV exposure. In such formulations, a doped silicon film can be produced by adding the disclosed group V element-containing compound in a ratio of 0.01% to 50% (by weight).

[0321] The disclosed formulation containing a Group V element-containing precursor can also be used to produce a doped silicon oxide film by any of the aforementioned wet coating methods by using oxidative curing after surface coating. Typical oxidative curing uses at least one of H2O (vapor), O2, O3, H2O2 and its plasma (and optionally an inert gas) at a temperature in the range of room temperature to 1000°C. Preferably, the curing comprises the following two-step process: soft baking at a temperature in the range of room temperature to 250°C and hard baking at a temperature in the range of 250°C to 1000°C. The hard baking step may be performed with or without the use of an oxidizing gas. For these wet coating applications, preferably A(Si x H 2x+1 It is advantageous to use a completely inorganic and low-volatility precursor selected from )3 (where x is 2 or greater and A = As or P).

[0322] Examples

[0323] The following non-limiting embodiments are provided to further illustrate embodiments of the invention. However, the embodiments are not intended to be all-encompassing and are not intended to limit the scope of the invention as described herein.

[0324] Example 1 Synthesis of (TMS)2P(Si3H7)

[0325] 3 g of Cl-Si3H7MCTS was added to a solution of 311 g of 10 wt% P(TMS) in hexane under magnetic stirring in a 20 mL vial. The reaction mixture was stirred at room temperature under an inert atmosphere for 5 days, during which all P(TMS)3 was converted to most P(TMS)2(Si3H7) in a 68% yield.

[0326] Example 2 Synthesis and Characterization of P(Si3H7)3

[0327] 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 stirring. The reaction mixture was refluxed at 68°C for 24 hours, during which all of the P(TMS)3 was converted to P(Si3H7)3 with a 93% yield. Fig. 1 This is the GC chromatogram of the reaction mixture of P(TMS)3+7 MCTS in hexane at 68°C for 24 hours.

[0328] Example 3 Synthesis of (TMS)P(SiH3)2

[0329] 35 g of 10 wt% P(TMS) in hexane was filled into 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 at 75°C for 24 hours in a sealed container, during which all of the P(TMS)3 was converted to most of the P(TMS)(SiH3)2 in a 59% yield.

[0330] Example 4. Synthesis of P(SiH3)3

[0331] 35.6 g of P(TMS) was filled into 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 which all of the P(TMS)3 was converted to most of the P(SiH3)3 with an 85% yield.

[0332] 235 g of P(TMS)3 was loaded into a leak-proof 600 mL Parr reactor. 183 g of monochlorosilane MCS was cryotrapped into the vessel. The reaction mixture was thawed and vigorously stirred at 400 rpm for 44 hours at 90°C, during which all of the P(TMS)3 was converted to most of the P(SiH3)3 in a 92% yield. Fig. 2 is the GC chromatogram of the reaction mixture of P(TMS)3+ and 3 MCS at 90°C for 44 hours.

[0333] Example 5 Synthesis of As(Si3H7)3

[0334] 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 hours in a 60 mL stainless steel container, only As(Si3H7)3 is produced with a yield of 75%. Fig. 3 This is the GC chromatogram of the reaction mixture of As(TMS)3+6 MCTS (Example 5) at 60°C for 24 hours.

[0335] Example 6 Synthesis of As(SiH3)(TMS)2

[0336] 34.5 g of As(TMS) was filled into 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 150 rpm at 90°C for 24 hours in a sealed container, during which most of the As(SiH3)(TMS)2 was obtained in a 52% yield.

[0337] Example 7 Synthesis of Sb(Si3H7)(TMS)2

[0338] Sb(Si3H7)(TMS)2 can be synthesized in 72% yield by reacting 32 g of Sb(TMS)2 with 7 g of MCTS at room temperature under vigorous magnetic stirring for one day. Heating at an elevated temperature (e.g., 50°C or 90°C) will result in decomposition.

[0339] Example 8 Synthesis of Sb(SiH3)(TMS)2

[0340] 32.8 g of Sb(TMS) was filled into a 60 mL stainless steel container. 9 g of monochlorosilane MCS was cryotrapped into the container. The reaction mixture was thawed and shaken at 150 rpm at 60°C for 24 hours in a sealed container, during which most of the Sb(SiH3)(TMS)2 was obtained in a 23% yield. Fig. 4 is the GC chromatogram of the reaction mixture of Sb(TMS)3 + 10 MCS at 60°C for 24 hours.

[0341] Example 9 Synthesis of P(Si2H5)3

[0342] 35 g of 10 wt% P(TMS) in hexane was filled into a 60 mL stainless steel container. 2.2 g of monochlorodisilane MCDS was added to the container. The reaction mixture was shaken at 150 rpm at 60°C for 24 hours in a sealed container, during which time P(Si2H5)3 was formed in a 22% yield.

[0343] Example 10 . Isolation of P(SiH3)3

[0344] 380 g of a synthetic mixture containing a product profile of 26% P(SiH3)3 in TMS-Cl solution was added to a 500 mL round-bottom flask inside a glove box. Standard fractional distillation was then performed. After removing volatile substances at 55–70°C, the main cut was collected under atmospheric pressure (its vapor phase temperature is in the range of 115–125°C), yielding 98% purity P(SiH3)375 g (representing a total yield of 76%). Further distillation or distillation with higher separation efficiency is expected to achieve >99%, preferably for industrial applications.

[0345] Processing Example 1: Synthesis of P(SiH3)2(Si3H7)

[0346] 10 g of 30 wt% of P(TMS)(SiH3)2 in TMS-Cl (e.g., synthesized by Example 3) was filled into a 60 mL stainless steel container. 2.0 g of MCTS was added to the container. The reaction mixture was shaken at 150 rpm at 75°C for 24 hours in a sealed container, during which time P(SiH3)2(Si3H7) was formed as the main product.

[0347] Processing Example 2: Synthesis of P(SiH3)(Si2H5)2

[0348] 118 g of P(TMS)3 was loaded into a leak-proof 600 mL Parr reactor. 31 g of monochlorosilane MCS was cryotrapped into the vessel. The reaction mixture was thawed and vigorously stirred at 400 rpm for 24 hours at 75°C, during which time all of the P(TMS)3 was converted to most of the P(SiH3)(TMS)2.

[0349] Approximately 25 wt% of P(SiH3)(TMS) in TMS-Cl was filled into a 60 mL stainless steel container. 2.4 g of MCDS was added to the container. The reaction mixture was shaken at 150 rpm at 60°C for 40 hours in a sealed container, during which time P(SiH3)(Si2H5)2 was formed as the major product.

[0350] Processing Example 3. CVD of a P-doped Si layer using precursor P(Si3H7)3

[0351] A P-doped Si layer is attempted to be deposited on a Si (100) substrate. P(Si3H7)3 vapor was introduced into a deposition reactor (heated to approximately 500°C) for 10 to 20 minutes at a flow rate of 10 sccm and a pressure of approximately 1 to 20 torr, during which time a polycrystalline P-doped silicon film with a thickness of 500 to 1500 Å was obtained. SEM images of the resulting P-doped silicon film can be obtained. Elemental analysis can be obtained using an energy dispersive X-ray analysis (EDAX) detector. AFM, XRD, and ellipsometric measurements of the resulting P-doped silicon film deposited on the Si (100) surface can be performed. Various other characterization techniques, such as atomic absorption (AA), MS-GC, NMR, FT-IR, neutron activation analysis (NAA), energy dispersive X-ray analysis (EDAX), Rutherford backscattering analysis (RBS), and X-ray analysis, can be used to characterize the deposited film.

[0352] Processing Example 4: Thermal CVD of a high-quality P-doped Si layer on a Si (100) wafer using precursor P(SiH3)2(Si3H7)

[0353] A Si (100) substrate that has been pre-etched with dilute HF acid and properly conditioned (rinsed and dried) is loaded into a deposition chamber, and then H2 baking is performed at 800–1000°C under a flow of 50–120 slm. Afterward, the substrate and chamber are equilibrated at 400–600°C and a back pressure of 20–50 torr. Then, pure H2 gas is bubbled into a liquid precursor P(SiH3)2(Si3H7) to deliver vapor of the P(SiH3)2(Si3H7) / H2 mixture to a 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 about 30–150 Å is deposited on a Si (100) wafer. Hydrogen residue can be confirmed to be absent according to RBS.

[0354] Processing Example 5 : Thermal CVD of P-doped Si films on Si (100) wafers using high-throughput precursor P(SiH3)(Si3H7)2

[0355] A Si (100) substrate that has been pre-etched with dilute HF acid and properly conditioned (rinsed and dried) is loaded into a deposition chamber, and then H2 baking is performed at 800–1000°C under a flow of 50–120 slm. Afterward, the substrate and chamber are equilibrated at approximately 550°C under a back pressure of 50 torr. Then, pure H2 gas is bubbled into the equilibrated liquid precursor P(SiH3)(Si3H7)2 at approximately 75°C and into the room temperature trisilane, and then introduced into a mixing chamber at approximately 100°C, and then the vapor of the P(SiH3)(Si3H7)2 / Si3H8 / H2 mixture is introduced into the reactor 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.

[0356] The subject matter of the claims described herein may be described in relation to exemplary embodiments for handling one or more computing application features / operations for a computing application having a user-interaction component, but the subject matter of the claims is not limited to these specific embodiments. Rather, the technology described herein may be applied to any suitable type of method, system, platform and / or device for managing the execution of a user-interaction component.

[0357] It will be understood that many additional modifications to the details, materials, steps, and arrangements of parts described and illustrated herein to illustrate the essence of the invention may be made by those skilled in the art within the principles and scope of the invention as set forth in the appended claims. Accordingly, the invention is not limited to the foregoing embodiments and / or specific embodiments of the accompanying drawings.

[0358] Although embodiments of the present invention have been illustrated and described, modifications thereof may be made by those skilled in the art without departing from the spirit or teaching of the present invention. The embodiments described herein are merely illustrative and non-limiting. Many variations and modifications of the composition and method are possible and are within the scope of the present invention. Accordingly, the scope of protection is not limited to the embodiments described herein, but is limited only by the following claims, which include all equivalents to the subject matter of the claims.

Claims

Claim 1 A method for forming a Si and group V element-containing film on a substrate, the method comprising: exposing the substrate to a vapor of a film-forming composition containing a Si and group V element-containing precursor; and forming a Si and group V element-containing film on the substrate by depositing at least a portion of the Si and group V element-containing precursor on the substrate via vapor deposition, wherein the Si and group V element-containing precursor has the following general chemical 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 (where, 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, n + p = 2 to 3; and R is C1 to C 10 , selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups; provided that 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). Claim 2 In claim 1, the group V element-containing precursor is P(SiH3)3, P(SiR3)(SiH3)2, P(SiR3)2(SiH3), P(SiR3)(Si2H5)2, P(SiR3)2(Si2H5), P(Si2H5)3, P(SiR3)(Si3H7)2, P(SiR3)2(Si3H7), P(Si3H7)3, As(SiH3)3, As(SiR3)(SiH3)2, As(SiR3)2(SiH3), As(SiR3)(Si2H5)2, As(SiR3)2(Si2H5), As(Si2H5)3, As(SiR3)(Si3H7)2, As(SiR3)2(Si3H7), As(Si3H7)3, Sb(SiH3)3, Sb(SiR3)(SiH3)2, Sb(SiR3)2(SiH3), Sb(SiR3)(Si2H5)2, Sb(SiR3)2(Si2H5), Sb(Si2H5)3, Sb(SIR3)(Si3H7)2, Sb(SiR3)2(Si3H7), Sb(Si3H7) 3, P(SiR3)(SiH3)(Si2H5), P(SiR3)(SiH3)(Si3H7), P(SiH3)2(Si2H5), P(SiH3)2(Si3H7), P(SiH3)(Si2H5)2, P(SiH3)(Si2H5)(Si3H7), P(SiH3)(Si3H7)2, P(Si2H5)2(Si3H7), P(Si2H5)(Si3H7)2, As(SiR3)(SiH3)(Si2H5), As(SiR3)(SiH3)(Si3H7), As(SiH3)2(Si2H5), As(SiH3)2(Si3H7), As(SiH3)(Si2H5)2, As(SiH3)(Si2H5)(Si3H7), As(SiH3)(Si3H7)2, A method selected from As(Si2H5)2(Si3H7), As(Si2H5)(Si3H7)2, Sb(SiR3)(SiH3)(Si2H5), Sb(SiR3)(SiH3)(Si3H7), Sb(SiH3)2(Si2H5), Sb(SiH3)2(Si3H7), Sb(SiH3)(Si2H5)2, Sb(SiH3)(Si2H5)(Si3H7), Sb(SiH3)(Si3H7)2, Sb(Si2H5)2(Si3H7), or Sb(Si2H5)(Si3H7)2, wherein R is selected from Me, Et, nPr, iPr, tBu, nBu, iBu, or sBu. Claim 3 In paragraph 2, the Si and group V element-containing precursors are, when R is Me, 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(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)(Si3H7), As(SiH3)(Si3H7)2, As(Si2H5)2(Si3H7), As(Si2H5)(Si3H7)2, A method selected from 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. Claim 4 The method of claim 1, wherein the Si and group V element-containing precursor 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. Claim 5 A method according to claim 1, wherein the film-forming composition is activated by plasma activating a Si and a group V element-containing precursor by heating a substrate to a temperature in the range of 200°C to 1000°C, or by a combination thereof. Claim 6 The method of claim 1 further comprises the step of exposing a substrate to a co-reactant, wherein the co-reactant is plasma-activated or not plasma-activated. Claim 7 A method according to any one of claims 1 to 6, further comprising the step of annealing a Si and group V element-containing layer through thermal annealing, furnace annealing, rapid thermal annealing, UV or e-beam curing, and / or plasma gas exposure. Claim 8 A method according to any one of claims 1 to 6, wherein the Si and group V element-containing film is a P-doped silicon-containing film. Claim 9 Film-forming composition for deposition of a film comprising a Si and a group V element-containing precursor having the following chemical 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 (where, 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, n + p = 2 to 3; and R is C1 to C 10 , selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups; provided that 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). Claim 10 A composition according to claim 9, wherein the purity of the Si and Group V element-containing precursor is > 98%. Claim 11 A wet film-forming composition for spin coating of a film comprising a Si and Group V element-containing precursor of claim 9 having five or more Si atoms. Claim 12 A wet film-forming composition according to claim 11, wherein the Si and group V element-containing precursor of claim 9 having the lowest volatility is selected to remain in the spun film during the annealing step and decompose in situ. Claim 13 A wet film-forming composition according to claim 11, further comprising a co-reactant which is a polysilane or a polysilane mixture having five or more silicon atoms. Claim 14 A wet film-forming composition according to claim 11, wherein the polysilane is cyclopentasilan or cyclohexasilane. Claim 15 A wet film-forming composition according to claim 11, wherein the spun film is an amorphous or polycrystalline Si film. Claim 16 A method for forming a Group V element-doped epitaxial Si film on a substrate, the method comprising: maintaining the substrate at a deposition temperature or a predetermined temperature near the deposition temperature; exposing the substrate to a mixture of vapor of a film-forming composition containing Si and a Group V element-containing precursor and vapor of a co-reactant polysilane; and forming a Group V element-doped epitaxial Si film on the substrate by depositing at least a portion of the Si and a Group V element-containing precursor on the substrate through a CVD process, wherein the Si and the Group V element-containing precursor have the following general chemical 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 (where, 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, n + p = 2 to 3; and R is C1 to C 10 , selected from linear, branched, or cyclic alkyl, alkenyl, and alkynyl groups; provided that 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). Claim 17 In paragraph 16, the co-reactant polysilane is Germanic, method. Claim 18 A method according to claim 16 or 17, wherein the predetermined temperature and deposition temperature are in the range of 200℃ to 1000℃.

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