Nitrogen-based oxygen-free dipoles, related devices, related systems, and related methods

Abstract

The techniques of the present disclosure generally relate to the field of semiconductor devices. More specifically, a semiconductor structure including a dipole layer including a metal and nitrogen containing film and a method of manufacturing the same. Related methods, deposition systems, and apparatuses are also described. The method for forming a semiconductor structure including a dipole layer includes the steps of: providing a substrate to a reaction chamber; contacting one or more metal precursors on at least part of the substrate by introducing the metal precursors into the reaction chamber; and reacting the deposited metal precursor with a nitrogen reactant in the reaction chamber, thereby forming a metal and nitrogen containing film on at least a portion of the substrate.

Description

Technical Field

[0001] The present disclosure generally relates to the field of semiconductor devices and more particularly to a semiconductor structure including a dipole layer and a method for manufacturing the same, the dipole layer including a metal nitride. Background Art

[0002] A transistor is an integrated circuit component or element that is usually formed on a semiconductor substrate. Specifically, modern integrated circuits contain field effect transistors (FETs), in which a current flows through a semiconductor channel between a source and a drain in response to a voltage applied to a control gate. The reduction in size of semiconductor devices (e.g., complementary metal oxide semiconductor (CMOS) devices) has led to a significant increase in the speed and density of modern integrated circuits. In advanced CMOS devices, including central processing units (CPUs) and systems on chip (SoCs), structures with multiple threshold voltages are required in order to optimize delay or power consumption. However, as device size decreases, providing a high-function structure with multiple threshold voltages faces severe challenges. For example, a particular problem is controlling the threshold voltage of a FET. Therefore, it is necessary to develop alternative materials to achieve better performance while reducing size. Summary of the invention

[0003] This summary is provided to introduce some concepts in a simplified form. These concepts are further described in detail in the detailed description of the example embodiments disclosed below. This summary is not intended to identify the key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0004] One aspect of the present disclosure relates to a method for forming a semiconductor structure including a dipole layer, the method comprising the following steps:

[0005] a) providing a substrate to a reaction chamber;

[0006] b) executing one or more loops, the loops comprising:

[0007] i. contacting one or more metal precursors with at least a portion of the substrate by introducing one or more metal precursors into the reaction chamber; and

[0008] ii. providing a nitrogen reactant into the reaction chamber;

[0009] A film containing metal and nitrogen is thereby formed on at least a portion of the substrate.

[0010] In certain embodiments, the methods disclosed herein provide a substrate comprising at least one of an interlayer and a high-k layer, wherein the method further comprises the step of annealing the substrate, thereby forming a dipole layer.

[0011] In certain embodiments, the methods disclosed herein provide for forming a film containing metal and nitrogen on an interlayer.

[0012] In certain embodiments, methods disclosed herein provide for forming a metal and nitrogen containing film on a high-k layer.

[0013] In certain embodiments, the methods disclosed herein provide that the cycle further comprises the step of providing an oxygen reactant into the reaction chamber to form a film comprising metal, oxygen, and nitrogen on at least a portion of the substrate.

[0014] In certain embodiments, the methods disclosed herein provide one or more metal precursors including an element selected from the group consisting of Mg, Ca, Sr, Ba, Al, Ga, In, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Re, Ge, Sb, Zn, and W.

[0015] In certain embodiments, the methods disclosed herein provide that one or more metal precursors include a ligand selected from the group consisting of amines, alkenyls, carbonyls, alkoxides, β-diketones, diazadienes, amidines, halogens, guanidinium salts, triazenes, carboxylates, cyclopentadienyls, and / or aryls.

[0016] In certain embodiments, the methods disclosed herein provide that the one or more metal precursors include a metal element selected from the group consisting of at least one of Ga and W.

[0017] In certain embodiments, the methods disclosed herein provide that the metal element is tungsten (W), and the one or more metal precursors are selected from the group consisting of at least one of formula (I), formula (II), and formula (III):

[0018]

[0019] Among them, Q 1 ,Q 2 ,Q 3 ,Q 4 ,Q 5 ,Q 6 Each independently selected from CO, F, Cl, Br, I, alkyl, alkenyl, N(R 1 )2, alkoxy, cycloalkoxy, cycloalkyl, aryl, arylalkyl, alkylaryl, cyclopentadienyl, alkyl-substituted cyclopentadienyl, and heteroalkyl; wherein each R 1 are independently selected from hydrogen, alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, and heteroalkyl.

[0020] In some embodiments, the methods disclosed herein provide Q 1 ,Q2 ,Q 3 ,Q 4 ,Q 5 ,Q 6 Each independently selected from CO, F, Cl, Br, I, C 1-8 Alkyl, C 2-8 Alkenyl, N(R 1 2. C 1-8 Alkoxy, C 3-8 Cycloalkoxy, C 3-8 Cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, C 1-8 Alkyl C 6-10 Aryl, cyclopentadienyl, C 1-8 Alkyl substituted cyclopentadienyl and heterocyclic C 1-8 Alkyl; wherein each R 1 are independently selected from hydrogen, C 1-8 Alkyl, C 3-8 Cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, C 1-8 Alkyl C 6-10 Aryl and heterocyclic C 1-8 alkyl.

[0021] In some embodiments, the methods disclosed herein provide Q 1 ,Q 2 ,Q 3 ,Q 4 ,Q 5 ,Q 6 Each independently selected from CO, F, Cl, Br, I, C 1-4 Alkyl, C 2-4 Alkenyl, N(R 1 2. C 1-4 Alkoxy, C 3-8 Cycloalkoxy, C 3-8 Cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-4 Alkyl, C 1-4 Alkyl C 6-10 Aryl, cyclopentadienyl, C 1-4 Alkyl substituted cyclopentadienyl and heterocyclic C 1-4 Alkyl; wherein each R 1 are independently selected from hydrogen, C 1-4 Alkyl, C 3-8 Cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-4 Alkyl, C1-4 Alkyl C 6-10 Aryl and heterocyclic C 1-4 alkyl.

[0022] In certain embodiments, the methods disclosed herein provide that the metal element is tungsten (W), and the one or more metal precursors are selected from WF6, WCl6, WBr6, WI6, W(CO)6, WF2(CO)4, WCl2(CO)4, WBr2(CO)4, W(Me)6, W(Et)6, W(nPr)6, W(nBu)6, W(tBu)6, W(NME2)6, W(NtBu)2(NMe2)4, W(NEt2)6, W(acac)2( CO)4,W(acac)1(CO)5,W(acac)3(CO)3,W(Pyr)6,W(benzene)(CO)5,W(toluene)(CO)5,W(cyclopentadienyl)(CO)5,W(naphthalene)(CO)5,WF5,WCl5,WBr5,WI5,W(CO)5,WF2(CO)3,WCl2(CO)3,WBr2(CO)3,W(Me)5,W(Et)5,W(nPr)5,W(nBu)5,W(tBu) 5,W(NME2)5,W(NtBu)2(NMe2)3,W(NEt2)5,W(acac)2(CO)3,W(acac)1(CO)4,W(acac)3(CO)2,W(Pyr)5,W(benzene)(CO)4,W(toluene)(CO)4,W(cyclopentadienyl)(CO)4,W(naphthalene)(CO)4,WF4,WCl4,WBr4,WI4,W(CO)4,WF2(CO)2,WCl2(CO)2,W Br2(CO)2, W(Me)4, W(Et)4, W(nPr)4, W(nBu)4, W(tBu)4, W(NME2)4, W(NtBu)2(NMe2)2, W(NEt2)4, W(acac)2(CO)2, W(acac)1(CO)3, W(acac)3(CO)1, W(Pyr)4, W(benzene)(CO)3, W(toluene)(CO)3, W(cyclopentadienyl)(CO)3 and W(naphthalene)(CO)3.

[0023] In certain embodiments, the methods disclosed herein provide that the metal element is gallium (Ga), and the one or more metal precursors are selected from the group of formula (IV):

[0024]

[0025] Among them, Q 7 ,Q 8 ,Q 9 Each independently selected from F, Cl, Br, I, alkyl, alkenyl, N(R2 )2, alkoxy, cycloalkoxy, cycloalkyl, aryl, arylalkyl, alkylaryl, R 3 NC(R 4 )NR 5 , R 6 NC[N(R 7 )2]NR 8 , R 9 N3R 10 , cyclopentadienyl, alkyl-substituted cyclopentadienyl, and heteroalkyl; wherein each R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,R 10 are independently selected from hydrogen, alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, and heteroalkyl.

[0026] In some embodiments, the methods disclosed herein provide Q 7 ,Q 8 ,Q 9 Each independently selected from F, Cl, Br, I, C 1-8 Alkyl, C 2-8 Alkenyl, N(R 2 2. C 1-8 Alkoxy, C 3-8 Cycloalkoxy, C 3-8 Cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, C 1-8 Alkyl C 6-10 Aryl, R 3 NC(R 4 )NR 5 , R 6 NC[N(R 7 )2]NR 8 , R 9 N3R 10 , cyclopentadienyl, C 1-8 Alkyl substituted cyclopentadienyl and heterocyclic C 1-8 Alkyl; wherein each R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,R 10 are independently selected from hydrogen, C 1-8Alkyl, C 3-8 Cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, C 1-8 Alkyl C 6-10 Aryl and heterocyclic C 1-8 alkyl.

[0027] In some embodiments, the methods disclosed herein provide Q 7 ,Q 8 ,Q 9 Each independently selected from F, Cl, Br, I, C 1-4 Alkyl, C 2-4 Alkenyl, N(R 2 2. C 1-4 Alkoxy, C 3-8 Cycloalkoxy, C 3-8 Cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-4 Alkyl, C 1-4 Alkyl C 6-10 Aryl, R 3 NC(R 4 )NR 5 , R 6 NC[N(R 7 )2]NR 8 , R 9 N3R 10 and cyclopentadienyl, C 1-4 Alkyl substituted cyclopentadienyl, heterocyclic C 1-4 Alkyl; wherein each R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,R 10 are independently selected from hydrogen, C 1-4 Alkyl, C3-8 cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-4 Alkyl, C 1-4 Alkyl C 6-10 Aryl and heterocyclic C 1-4 alkyl.

[0028] In a specific embodiment, the method disclosed herein provides that the metal element is gallium (Ga), and one or more metal precursors are selected from GaF3, GaCl3, GaBr3, GaI3, Ga(Me)3, Ga(Et)3, Ga(nPr)3, Ga(nBu)3, Ga(tBu)3, Ga(NMe2)3, Ga(NtBu)2(NMe2)1, Ga(NtBu)1(NMe2)2, Ga(NEt2)3, Ga(Pyr)3, Ga(guanidine)3 and Ga(triazene)3.

[0029] In certain embodiments, the methods disclosed herein provide that the nitrogen reactant is selected from N(R 11 )3 and (R 12 )NN(R 13 ), where each R 11 ,R 12 ,R 13 independently selected from hydrogen, alkyl, alkenyl, cycloalkyl and Si(R 14 )3; where R 14 is selected from alkyl, alkenyl, alkoxy and Si(R 15 )3; and wherein R 15 Selected from alkyl, alkenyl and alkoxy.

[0030] In some embodiments, the methods disclosed herein provide that each R 11 ,R 12 ,R 13 are independently selected from hydrogen, C 1-8 Alkyl, C 2-8 Alkenyl, Ring C 3-8 Alkyl and Si(R 14 )3, where R 14 Selected from C 1-8 Alkyl, C 2-8 Alkenyl, C 1-8 Alkoxy and Si(R 15 )3; and wherein R 15 Selected from C 1-8 Alkyl, C 2-8 Alkenyl and C 1-8 Alkoxy.

[0031] In some embodiments, the methods disclosed herein provide that each R 11 ,R 12 ,R 13 are independently selected from hydrogen, C 1-4 Alkyl, C 2-4 Alkenyl, Ring C 3-8 Alkyl and Si(R 14 )3, where R 14 Selected from C 1-4 Alkyl, C2-4 Alkenyl, C 1-4 Alkoxy and Si(R 15 )3; and wherein R 15 Selected from C 1-4 Alkyl, C 2-4 Alkenyl and C 1-4 Alkoxy.

[0032] In a particular embodiment, the method disclosed herein provides a nitrogen reactant selected from the group including at least one of the following: NH3, diazene (N2H2), hydrazine (N2H4), methylhydrazine (N2MeH3), ethylhydrazine (N2EtH3), propylhydrazine (N2nPrH3), butylhydrazine (N2nBuH3), tert-butylhydrazine (N2tBuH3), 1,1-dimethylhydrazine (N2Me2H2), 1,1-diethylhydrazine (N2Et2H2), 1,1-dipropylhydrazine (N2nPr2H2), 1,1-dibutylhydrazine (N2nBu2H2), trimethylsilylhydrazine (N2[Si(Me)3]H2) and tris(trimethylsilyl)silylhydrazine (N2[Si(Si(Me)3)3]H2).

[0033] In certain embodiments, the methods disclosed herein provide that the oxygen reactant is selected from the group consisting of at least one of: H2O, D2O, H2O2, O3, O2, N2O, NO, N2O5, SO2, oxygen-containing plasma, and oxygen radicals.

[0034] In certain embodiments, the methods disclosed herein provide that the metal and nitrogen containing film includes at least one of gallium nitride (GaN) and tungsten nitride (WN).

[0035] In certain embodiments, the methods disclosed herein provide that the metal, oxygen, and nitrogen containing film includes at least one of gallium oxynitride (GaON) and tungsten oxynitride (WON).

[0036] In certain embodiments, the methods disclosed herein comprise at least 1 cycle to at most 1000 cycles, preferably at least 2 cycles to at most 100 cycles.

[0037] In certain embodiments, the methods disclosed herein provide a cycle comprising one or more pulses of a metal precursor and one or more pulses of a nitrogen reactant.

[0038] In certain embodiments, the methods disclosed herein provide that each pulse is followed by a purge with an inert gas selected from at least one of N 2 and a noble gas.

[0039] In certain embodiments, the methods disclosed herein provide a dipole layer having an average thickness of 1 nm or less.

[0040] In certain embodiments, the methods disclosed herein provide that one or more cycles comprising the steps of contacting one or more metal precursors with at least a portion of a substrate and providing a nitrogen reactant into a reaction chamber are completely oxygen-free.

[0041] In certain embodiments, the methods disclosed herein provide contacting a ligand compound with one or more metal precursors with at least a portion of a substrate.

[0042] In certain embodiments, the methods disclosed herein provide a ligand compound selected from the group consisting of XN(R 16 )2 and at least one of β-diketone; wherein X is hydrogen or an alkali metal selected from Li, Na, K and Rb; and wherein R 16 Selected from alkyl and Si(R 17 )3; and wherein R 17 Selected from alkyl, alkenyl and alkoxy.

[0043] In some embodiments, the methods disclosed herein provide R 16 Selected from C 1-8 Alkyl and Si(R 17 )3; and wherein R 17 Selected from C 1-8 Alkyl, C 2-8 Alkenyl and C 1-8 Alkoxy.

[0044] In some embodiments, the methods disclosed herein provide R 16 Selected from C 1-4 Alkyl and Si(R 17 )3; and wherein R 17 Selected from C 1-4 Alkyl, C 2-4 Alkenyl and C 1-4 Alkoxy.

[0045] In certain embodiments, the methods disclosed herein provide that the ligand compound is a dialkyldisilazane or a salt thereof.

[0046] In certain embodiments, the methods disclosed herein provide that the ligand compound is selected from acetylacetonate, 2,2,6,6-tetramethylheptane-3,5-dioate, and 1,1,1,5,5,5-hexafluoropentane-2,4-dioate.

[0047] In certain embodiments, the methods disclosed herein provide that one or more metal precursors are metal bis(arene) precursors, wherein the arene ligand is η6-benzene or an η6-benzene derivative.

[0048] In certain embodiments, the methods disclosed herein provide that the cycle further comprises the step of providing an organic molecule reactant comprising at least one halogen group into the reaction chamber before or after providing the nitrogen reactant.

[0049] In certain embodiments, the methods disclosed herein provide that the organic molecule reactant is selected from the group consisting of formula (V):

[0050]

[0051] Among them, Q 10 ,Q 11 ,Q 12 ,Q 13 are each independently selected from hydrogen, halogen, alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkoxy, and heteroalkyl; and wherein, Q 10 ,Q 11 ,Q 12 ,Q 13 At least one of them is a halogen.

[0052] In some embodiments, the methods disclosed herein provide Q 10 ,Q 11 ,Q 12 ,Q 13 are each independently selected from hydrogen, halogen, C 1-8 Alkyl, C 1-8 Alkenyl, C 3-8 Cycloalkyl, C 6-10 Aryl, C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, C 1-8 Alkoxy and heterocyclic C 1-8 alkyl; and wherein Q 10 ,Q 11 ,Q 12 ,Q 13 At least one of them is a halogen.

[0053] In some embodiments, the methods disclosed herein provide Q 10 ,Q 11 ,Q 12 ,Q 13 are each independently selected from hydrogen, halogen, C 1-4 Alkyl, C 1-4 Alkenyl, C 3-8 Cycloalkyl, C 6-10 Aryl, C 1-4 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-4 Alkyl, C 1-4Alkoxy and heterocyclic C 1-4 alkyl; and wherein Q 10 ,Q 11 ,Q 12 ,Q 13 At least one of them is F, Cl, Br or I.

[0054] In certain embodiments, the methods disclosed herein provide that the organic molecule reactant is selected from methyl chloride (CH3Cl), methyl bromide (CH3Br), methyl iodide (CH3I), dichloromethane (CH2Cl2), dibromomethane (CH2Br2), diiodomethane (CH2I2), trichloromethane (CHCl3), tribromomethane (CHBr3), triiodoform (CHI3), ethyl chloride (C2H5Cl), ethyl bromide (C2H5Br), ethyl iodide (C2H5I), 1,2-dichloroethane (C2H4Cl2), 1,2-dibromoethane (C2H4Br2), 1,2-diiodoethane (C2H4I2), propyl chloride (C3H7Cl), , bromopropane (C3H7Br), iodopropane (C3H7I), 1,3-dichloropropane (C3H6Cl2), 1,3-dibromopropane (C3H6Br2), 1,3-diiodopropane (C3H6I2), chlorobutane (C4H9Cl), bromobutane (C4H9Br), iodobutane (C4H9I), 1,4-dichlorobutane (C4H8Cl2), 1,4-dibromobutane (C4H8Br2), 1,4-diiodobutane (C4H8I2), benzyl chloride (C7H7Cl), benzyl bromide (C7H7Br), benzyl iodide (C7H7I), chlorobenzene (C6H5Cl), bromobenzene (C6H5Br) and iodobenzene (C6H5I).

[0055] In certain embodiments, the methods disclosed herein provide that the substrate comprises silicon or silicon oxide.

[0056] In certain embodiments, the methods disclosed herein further include the step of forming a high-κ dielectric on the dipole layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the size of some elements in the drawings may be exaggerated relative to other elements to help improve the understanding of the illustrated embodiments of the present disclosure.

[0058] Figure 1An exemplary embodiment of a method for forming a semiconductor structure including a dipole layer is described. The method begins 111 after a substrate has been provided to a reaction chamber. A cyclic deposition process includes contacting one or more metal precursors with at least a portion of the substrate with a metal precursor pulse 112. Optionally, after the metal precursor pulse 112, the reaction chamber is purged 113. Then, a nitrogen reactant is provided to the reaction chamber with a nitrogen reactant pulse 114. Optionally, after the nitrogen reactant pulse, the reaction chamber can be purged 115. The metal precursor pulse 112, the nitrogen reactant pulse 114, and the optional purges 113, 115 can be repeated 116 any number of times to obtain a metal nitride-containing film having a desired thickness. When a metal nitride-containing layer having a desired thickness has been deposited, the method ends 117. Once the method ends, the substrate can, for example, be subjected to additional processes to form a device structure and / or device.

[0059] Figure 2 An exemplary embodiment of a method for forming a semiconductor structure including a dipole layer is described. The method begins 211 after a substrate has been provided to a reaction chamber. A cyclic deposition process includes providing a nitrogen reactant to the reaction chamber in a nitrogen reactant pulse 212. Optionally, after the nitrogen reactant pulse 212, the reaction chamber is purged 213. Then, one or more metal precursors are contacted with at least a portion of the substrate in a metal precursor pulse 214. Optionally, the reaction chamber can be purged 215 after the metal precursor pulse. The nitrogen reactant pulse 212, the metal precursor pulse 214, and the optional purges 213, 215 can be repeated 216 any number of times to obtain a film containing a metal nitride having a desired thickness. When a layer containing a metal nitride having a desired thickness has been deposited, the method ends 217. Once the method ends, the substrate can, for example, be subjected to additional processes to form a device structure and / or a device.

[0060] Figure 3Another exemplary embodiment of the present disclosure is shown. The method begins 311 after a substrate has been provided to a reaction chamber. The cyclic deposition process includes contacting one or more metal precursors with at least a portion of the substrate with a metal precursor pulse 312. Optionally, after the metal precursor pulse 312, the reaction chamber is purged 313. Then, a nitrogen reactant is provided to the reaction chamber with a nitrogen reactant pulse 314. Optionally, after the nitrogen reactant pulse, the reaction chamber can be purged 315. Then, an oxygen reactant is provided to the reaction chamber with an oxygen reactant pulse 316. Optionally, after the oxygen reactant pulse, the reaction chamber can be purged 317. The metal precursor pulse 312, the nitrogen reactant pulse 314, the oxygen reactant pulse 316 and the optional purges 313, 315, 317 can be repeated 318 any number of times to obtain a metal oxynitride-containing film having a desired thickness. When a metal oxynitride-containing layer having a desired thickness has been deposited, the method ends 319. Once the method is concluded, the substrate may, for example, be subjected to additional processes to form device structures and / or devices.

[0061] Figure 4 Another exemplary embodiment of the present disclosure is shown. The method starts 411 after the substrate has been provided to the reaction chamber. The cyclic deposition process includes providing nitrogen reactants to the reaction chamber with nitrogen reactant pulses 412. Optionally, after the nitrogen reactant pulse 412, the reaction chamber is purged 413. Then, one or more metal precursors are contacted with at least a portion of the substrate with a metal precursor pulse 414. Optionally, the reaction chamber can be purged 415 after the metal precursor pulse. Then, oxygen reactants are provided to the reaction chamber with oxygen reactant pulses 416. Optionally, after the oxygen reactant pulse, the reaction chamber can be purged 417. The nitrogen reactant pulse 412, the metal precursor pulse 414, the oxygen reactant pulse 416, and the optional purges 413, 415, 417 can be repeated 418 any number of times to obtain a film containing metal oxynitride having a desired thickness. When a layer containing metal oxynitride having a desired thickness has been deposited, the method ends 419. Once the method ends, the substrate can, for example, be subjected to additional processes to form a device structure and / or device.

[0062] like Figures 1 to 4 As shown, each metal precursor pulse, nitrogen reactant pulse and / or oxygen reactant pulse has a sequential order. However, unless otherwise stated, the methods disclosed herein are not limited to the pulse order described. For example, the order of each pulse during each cycle can be changed depending on the application.

[0063] Figure 5 A system 500 is shown according to another exemplary embodiment of the present disclosure. The system 500 can be used to perform the methods described herein and / or form part of the structures or devices described herein.

[0064] In the illustrated example, system 500 includes one or more reaction chambers 502, a metal precursor gas source 504, a nitrogen reactant gas source 506, a purge gas source 508, an exhaust 510, and a controller 512. Reaction chamber 502 can include any suitable reaction chamber, such as an ALD or CVD reaction chamber. Optionally, system 500 includes additional gas sources, such as a gas source 505 containing an oxygen reactant.

[0065] Metal precursor gas source 504 may include a container and one or more precursors as described herein, either alone or mixed with one or more carrier gases (e.g., inert gases). Nitrogen reactant gas source 506 may include a container and one or more nitrogen reactants as described herein, either alone or mixed with one or more carrier gases. Purge gas source 508 may include one or more inert gases, such as N2 or a rare gas, as described herein. System 500 may include any suitable number of gas sources. Gas sources 504-508 may be coupled to reaction chamber 502 via lines 514-518, which may each include a flow controller, a valve, a heater, etc. Exhaust 510 may include one or more vacuum pumps.

[0066] The controller 512 includes electronic circuits and software to selectively operate valves, manifolds, heaters, pumps, and other components included in the system 500. Such circuits and components are used to introduce precursors, reactants, and purge gases from the corresponding sources 504-508. The controller 512 can control the timing of gas pulse sequences, the temperature of the substrate and / or the reaction chamber, the pressure in the reaction chamber, and various other operations to provide the correct operation of the system 500. The controller 512 may include control software to control the flow of precursors, reactants (i.e., nitrogen reactants and / or oxygen reactants) and purge gases into and out of the reaction chamber 502 by electrically or pneumatically controlling valves. The controller 512 may include modules that perform certain tasks, such as software or hardware components, such as FPGAs or ASICs. The modules may be advantageously configured to reside on an addressable storage medium of the control system and configured to perform one or more processes.

[0067] Other configurations of the system 500 are possible, including different numbers and types of precursor and reactant sources and purge gas sources. In addition, it should be understood that there are many arrangements of valves, conduits, precursor sources, and purge gas sources that can be used to achieve the goal of selectively supplying gases into the reaction chamber 502. In addition, as a schematic representation of the system, many components have been omitted for simplicity of illustration, and these components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0068] During operation of reactor system 500, a substrate, such as a semiconductor wafer (not shown), is transferred from, for example, a substrate handling system to reaction chamber 502. Once the substrate is transferred to reaction chamber 502, one or more gases, such as precursors, reactants, carrier gases, and / or purge gases, are introduced into reaction chamber 502 from gas sources 504-508.

[0069] Figure 6 A graphical representation of the chemical resistance to TiCl4 and NH3 etching of a film deposited on a substrate according to the methods described herein, wherein the film comprises gallium and nitrogen (eg, GaN). DETAILED DESCRIPTION

[0070] Although certain embodiments and examples are disclosed below, those skilled in the art will appreciate that the disclosure extends beyond the specifically disclosed embodiments and / or uses of the disclosure and obvious modifications and equivalents thereof. Therefore, it is intended that the scope of the disclosure disclosed should not be limited by the specifically disclosed embodiments described below.

[0071] In the following detailed description, the underlying technology of the present disclosure will be described through different aspects of the present disclosure. It will be readily understood that the various aspects of the present disclosure, as generally described herein and shown in the accompanying drawings, may be arranged, replaced, combined and designed in a variety of different configurations, all of which are expressly intended and form part of the present disclosure. This description is intended to help the reader more easily understand the technical concepts, but is not meant to limit the scope of the present disclosure, which is limited only by the claims.

[0072] References throughout this specification to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in conjunction with the embodiment is included in at least one embodiment of the present disclosure. Therefore, the phrases "in one embodiment" or "in an embodiment" appearing in various places in this specification do not necessarily all refer to the same embodiment.

[0073] As used herein, the term "includes" and its variations are synonymous with "comprises" and its variations or "contains" and its variations, and are inclusive or open-ended and do not exclude additional, unlisted components, elements, or method steps. The term "includes" and its variations, when referring to the components, elements, or method steps, also include embodiments consisting of the components, elements, or method steps. The singular forms "a", "an", and "the" include singular and plural referents unless the context clearly dictates otherwise.

[0074] The objects described herein as "connected" or "coupled" reflect a functional relationship between the objects being described, that is, the term indicates that the objects being described must be connected in a manner to perform the specified function, which may be direct or indirect connection, in an electrical or non-electrical (i.e., physical) manner, as appropriate to the context in which the term is used.

[0075] As used herein, the term "substantially" refers to the complete or nearly complete extent or degree of an action, characteristic, property, state, structure, item, or result. For example, a "substantially" closed object means that the object is completely closed or nearly completely closed. In some cases, the exact degree of deviation from absolute completeness that is permitted may depend on the circumstances. Generally speaking, however, near completion will have the same overall result as if absolute and complete completion were obtained. When used in a negative sense, the use of "substantially" also applies to referring to the complete or nearly complete absence of an action, characteristic, property, state, structure, item, or result.

[0076] As used herein, the term "about" is used to provide flexibility to a numerical value or a range endpoint, and a given value can be "slightly above" or "slightly below" the value or endpoint, depending on the specific circumstances. Unless otherwise specified, the term "about" used in accordance with a specific numerical value or numerical range should also be understood to support such numerical terms or ranges without the term "about". For example, the expression "about 30" should be interpreted as supporting not only values ​​slightly above and slightly below 30, but also the actual numerical value of 30.

[0077] Numerical ranges listed by endpoints include all integers, and where appropriate, include fractions within the range (e.g., 1 to 5 may include 1, 2, 3, 4 when involving, for example, multiple elements, and may also include 1.5, 2, 2.75, and 3.80 when involving, for example, measured values). The description of endpoints also includes the endpoint values ​​themselves (e.g., 1.0 to 5.0 includes 1.0 and 5.0). Any numerical range listed herein is intended to include all subranges contained therein. In addition, the terms first, second, third, etc. in the specification and claims are used to distinguish similar elements, and are not necessarily used to describe continuous or chronological order, unless otherwise specified. It should be understood that the terms used in this manner are interchangeable where appropriate, and the embodiments of the present disclosure described herein can operate in other sequences different from those described or shown herein.

[0078] In this specification, reference may be made to devices, structures, systems, or methods that provide "improved" performance (e.g., increased or decreased results, as the case may be). It should be understood that, unless otherwise stated, such "improvement" is a measure of the benefit obtained based on a comparison with a device, structure, system, or method in the prior art. In addition, it should be understood that the degree of improved performance may vary between the disclosed embodiments, and equality or consistency in the amount, degree, or implementation of improved performance should not be assumed to be universally applicable.

[0079] In addition, embodiments of the present disclosure may include hardware, software, and electronic components or modules, which, for purposes of discussion, may be illustrated and described as if most of the components were implemented only in hardware. However, those skilled in the art will recognize, based on a reading of this detailed description, that in at least one embodiment, the electronic-based aspects of the present invention may be implemented in software (e.g., instructions stored on a non-transitory computer-readable medium) that may be executed by one or more processing units (e.g., microprocessors and / or application-specific integrated circuits). Therefore, it should be noted that the technology of the present disclosure may be implemented using multiple hardware- and software-based devices and multiple different structural components. For example, the "server" and "computing device" described in the specification may include one or more processing units, one or more computer-readable media modules, one or more input / output interfaces, and various connections of connecting components.

[0080] Reference to substituents throughout this specification means that one or more hydrogen atoms on the atom designated in the expression "substituted" are replaced with a group selected from the designated group as detailed below, provided that the normal valence of the designated atom is not exceeded and that the substitution results in a chemically stable compound, i.e., a compound that is sufficiently stable to survive isolation from a reaction mixture.

[0081] The term "halo" or "halogen" as a group or part of a group is a generic term for fluorine (F), chlorine (Cl), bromine (Br), iodine (I).

[0082] The term "alkyl" as a group or part of a group refers to a group of formula C n H 2n+1 wherein n is a number greater than or equal to 1. The alkyl group may be straight or branched and may be substituted as indicated herein. Typically, the alkyl groups disclosed herein contain 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. When a subscript is used after a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. For example, the term "C 1-20 "Alkyl" as a group or part of a group refers to a group of the formula -C n H 2n+1 wherein n is a number from 1 to 20. Thus, for example, "C 1-8 "Alkyl" includes all straight or branched chain alkyl groups having between 1 and 8 carbon atoms, thus including methyl, ethyl, n-propyl, isopropyl, butyl and isomers thereof (e.g., n-butyl, isobutyl and tert-butyl); pentyl and isomers thereof, hexyl and isomers thereof, etc. "Substituted alkyl" refers to an alkyl group substituted with one or more substituents (e.g., 1 to 3 substituents, e.g., 1, 2 or 3 substituents) at any available point of attachment.

[0083] When the suffix "ene" is used in conjunction with an alkyl group, i.e., "alkylene", this refers to an alkyl group as defined herein having two single bonds as points of attachment to other groups. As used herein, the term "alkylene" is also known as "alkanediyl" and, by itself or as part of another substituent, refers to a divalent alkyl group, i.e., having two single bonds for attachment to two other groups. Alkylene groups may be straight or branched and may be substituted as indicated herein. Non-limiting examples of alkylene groups include methylene (-CH2-), ethylene (-CH2-CH2-), methylmethylene (-CH(CH3)-), 1-methylethylene (-CH(CH3)-CH2-), n-propylene (-CH2-CH2-CH2-), 2-methylpropylene (-CH2-CH(CH3)-CH2-), 3-methylpropylene (-CH2-CH2-CH(CH3)-), n-butene (-CH2-CH2-CH2-CH2-), 2-methylbutylene (-CH2-CH(CH3)-CH2-CH2-), 4-methylbutene (-CH2-CH2-CH2-CH(CH3)-), pentyl and its chain isomers, hexyl and its chain isomers.

[0084] The term "alkenyl" as a group or part of a group refers to an unsaturated hydrocarbon group, which may be straight or branched, containing one or more carbon-carbon double bonds. Typically, the alkenyl groups disclosed herein contain 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms. When a subscript is used after a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. 3-20 Examples of alkenyl groups are ethenyl, 2-propenyl, 2-butenyl, 3-butenyl, 2-pentenyl and isomers thereof, 2-hexenyl and isomers thereof, 2,4-pentadienyl and the like.

[0085] The term "cycloalkyl" as a group or part of a group refers to a cyclic alkyl group, i.e., a monovalent saturated hydrocarbon group having one or more ring structures, containing 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms; more preferably 3 to 6 carbon atoms. Cycloalkyl includes all saturated hydrocarbon groups containing one or more rings, including monocyclic, bicyclic or tricyclic rings. The other rings of a polycyclic cycloalkyl group may be fused, bridged and / or connected by one or more spiro atoms. When a subscript is used after a carbon atom in this document, the subscript refers to the number of carbon atoms that the named group may contain. For example, the term "C 3-20 Cycloalkyl” refers to a cyclic alkyl group containing 3 to 20 carbon atoms. For example, the term “C 3-10 Cycloalkyl” refers to a cyclic alkyl group containing 3 to 10 carbon atoms. For example, the term “C 3-8 Cycloalkyl” refers to a cyclic alkyl group containing 3 to 8 carbon atoms. For example, the term “C 3-6Cycloalkyl" is a cyclic alkyl group containing 3 to 6 carbon atoms. 3-12 Examples of cycloalkyl include, but are not limited to, adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]hept-2-yl, (1S,4R)-norbornan-2-yl, (1R,4R)-norbornan-2-yl, (1S,4S)-norbornan-2-yl, (1R,4S)-norbornan-2-yl.

[0086] When the suffix "" is used in conjunction with a cycloalkyl group, i.e., cycloalkylene, this refers to a cycloalkyl group as defined herein having two single bonds as points of attachment to other groups. Non-limiting examples of "cycloalkylene" include 1,2-cyclopropylene, 1,1-cyclopropylene, 1,1-cyclobutene, 1,2-cyclobutene, 1,3-cyclopentylene, 1,1-cyclopentylene, and 1,4-cyclohexylene.

[0087] When an alkylene or cycloalkylene group is present, the connection to the molecular structure forming part thereof may be through a common carbon atom or different carbon atoms. To illustrate this, using the asterisk nomenclature of the present disclosure, a C3 alkylene group may be, for example, *-CH2CH2CH2-*, *-CH(-CH2CH3)-*, or *-CH2CH(-CH3)-*. Similarly, a C3 cycloalkylene group may be:

[0088]

[0089] The term "aryl" as a group or part of a group refers to a polyunsaturated aromatic hydrocarbon radical having a single ring (i.e., phenyl) or multiple aromatic rings fused together (e.g., naphthyl), or covalently linked, typically containing 6 to 20 atoms; preferably 6 to 10, wherein at least one ring is aromatic. The aromatic ring may optionally include one or two additional rings (cycloalkyl, heterocyclyl, or heteroaryl) fused thereto. Examples of suitable aryl groups include C 6-20 Aryl, preferably C 6-10 Aryl, more preferably C 6-8 Aryl. Non-limiting examples of aryl groups include phenyl, biphenyl, biphenyl or 1- or 2-naphthyl; 1-, 2-, 3-, 4-, 5- or 6-tetrahydronaphthyl (also known as "1,2,3,4-tetrahydronaphthalene"); 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-azulyl, 4-, 5-, 6 or 7-indenyl; 4- or 5-indanyl; 5-, 6-, 7- or 8-tetrahydronaphthyl; 1,2,3,4-tetrahydronaphthyl; and 1,4-dihydronaphthyl; 1-, 2-, 3-, 4- or 5-pyrenyl. "Substituted aryl" refers to an aryl group having one or more substituents (e.g., 1, 2 or 3 substituents, or 1 to 2 substituents) at any available attachment point.

[0090] The term "alkoxy" or "alkyloxy" as a group or part of a group refers to a radical having the formula -OR b A group in which R b is an alkyl group as defined above. Non-limiting examples of suitable alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy and hexyloxy.

[0091] The term "cycloalkoxy" as a group or part of a group refers to a cycloalkoxy radical having the formula -OR c A group in which R c is a cycloalkyl group as defined above.

[0092] The term "aryl" as a group or part of a group refers to a polyunsaturated aromatic hydrocarbon radical having a single ring (i.e., phenyl) or multiple aromatic rings fused together (e.g., naphthyl), or covalently linked, typically containing 6 to 20 atoms; preferably 6 to 10, wherein at least one ring is aromatic. The aromatic ring may optionally include one or two additional rings (cycloalkyl, heterocyclyl, or heteroaryl) fused thereto. Examples of suitable aryl groups include C 6-20 Aryl, preferably C 6-10 Aryl, more preferably C 6-8 Aryl. Non-limiting examples of aryl groups include phenyl, biphenyl, biphenyl or 1- or 2-naphthyl; 1-, 2-, 3-, 4-, 5- or 6-tetrahydronaphthyl (also known as "1,2,3,4-tetrahydronaphthalene"); 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-azulyl, 4-, 5-, 6 or 7-indenyl; 4- or 5-indanyl; 5-, 6-, 7- or 8-tetrahydronaphthyl; 1,2,3,4-tetrahydronaphthyl; and 1,4-dihydronaphthyl; 1-, 2-, 3-, 4- or 5-pyrenyl. "Substituted aryl" refers to an aryl group having one or more substituents (e.g., 1, 2 or 3 substituents, or 1 to 2 substituents) at any available attachment point.

[0093] The term "arylalkyl" as a group or part of a group refers to an alkyl group as defined herein, wherein at least one hydrogen atom is substituted by at least one aryl group as defined herein. Non-limiting examples of arylalkyl include benzyl, phenethyl, dibenzylmethyl, methylphenylmethyl, 3-(2-naphthyl)-butyl, and the like.

[0094] The term "alkylaryl" as a group or part of a group refers to an aryl group as defined herein, wherein at least one hydrogen atom is replaced by at least one alkyl group as defined herein. Non-limiting examples of alkylaryl groups include p-CH3-R d -, where R d is aryl as defined above.

[0095] The term "heteroalkyl" as a group or part of a group refers to an acyclic alkyl group in which one or more carbon atoms are replaced by at least one heteroatom selected from O, Si, S, B and P, with the proviso that the chain cannot contain two adjacent heteroatoms. This means that one or more -CH3 of the acyclic alkyl group may be replaced by, for example, -OH, and / or one or more -CR2- of the acyclic alkyl group may be replaced by O, Si, S, B and P.

[0096] In the present disclosure, "gas" may include materials that are gaseous at normal temperature and pressure (NTP), evaporated solids and / or evaporated liquids, and may be composed of a single gas or a gas mixture depending on the circumstances. Gases other than process gases, i.e., gases that are not introduced through gas distribution components, other gas distribution devices, etc., may be used, for example, to seal reaction spaces, and may include sealing gases, such as rare gases. In some cases, the term "precursor" may refer to a compound that participates in a chemical reaction to produce another compound, particularly a compound that constitutes a membrane matrix or a main skeleton of a membrane; the term "reactant" may be used interchangeably with the term precursor.

[0097] As used herein, the term "substrate" may refer to any one or more underlying materials that may be used to form or on which a device, circuit, or film may be formed. A "substrate" may be continuous or non-continuous; rigid or flexible; solid or porous; and combinations thereof. A substrate may be in any form, such as a powder, a plate, or a workpiece. Plate-like substrates may include wafers of various shapes and sizes. A substrate may include a bulk material, such as silicon (e.g., single crystal silicon), other Group IV materials, such as germanium, or other semiconductor materials, such as Group II-VI or Group III-V semiconductor materials, and may include one or more layers covering or underlying the bulk material. In addition, the substrate may include various features, such as depressions, protrusions, etc., formed in or on at least a portion of a substrate layer. For example, a substrate may include a bulk semiconductor material and an insulating or (high-k) dielectric material layer covering at least a portion of the bulk semiconductor material.

[0098] As used herein, the terms "film" and / or "layer" may refer to any continuous or discontinuous structure and material, such as materials deposited by the methods disclosed herein. For example, the film and / or layer may include a two-dimensional material, a three-dimensional material, nanoparticles, or even a partial or complete molecular layer or a partial or complete atomic layer or atom and / or molecular clusters, or a layer composed of isolated atoms and / or molecules. The film or layer may include a material or layer having pinholes, which may be continuous or discontinuous.

[0099] In the present disclosure, the following abbreviations of chemical structures are used: Cp represents cyclopentadienyl, Me represents methyl; Et represents ethyl; nPr represents n-propyl; nBu represents n-butyl; tBu represents tert-butyl; acac represents acetylacetonate.

[0100] In general, the technology disclosed herein relates to the field of semiconductor devices, and more specifically, to a method for forming a semiconductor structure including a dipole layer, which is used to produce several electronic components such as microprocessors, integrated circuit chips, and memory chips. The important steps of semiconductor formation mentioned here can include forming a film containing metal and nitrogen, such as a metal nitride film, or a layer on the insulating material below, such as a high-k dielectric (or gate dielectric) or silicon oxide (or gate oxide). Advantageously, the inventors have found that the method disclosed herein allows the removal of any oxygen or carbon contamination during the deposition of the film containing metal and nitrogen, resulting in a stable nitrogen-rich layer with a lower thickness. In detail, one of the challenges in semiconductor formation, especially field effect transistors, is to reduce the equivalent oxide thickness (EOT) of the gate dielectric or gate oxide, and avoid leakage current to the gate terminal. Compared with the prior art, the present disclosure allows the reduction of EOT while achieving high capacitance and improved electrical performance of semiconductor devices.

[0101] As explained in more detail below, various embodiments of the present disclosure are directed to a method for forming a semiconductor structure including a dipole layer, the method comprising the following steps:

[0102] a) providing a substrate to a reaction chamber;

[0103] b) executing one or more loops, the loops comprising:

[0104] i. contacting one or more metal precursors with at least a portion of the substrate by introducing one or more metal precursors into the reaction chamber; and

[0105] ii. providing a nitrogen reactant into the reaction chamber;

[0106] A film containing metal and nitrogen is thereby formed on at least a portion of the substrate.

[0107] As used herein, the term "semiconductor structure" or "semiconductor device" refers to an electronic component that relies on the electronic properties of semiconductor materials to achieve its function. The electrical conductivity of semiconductors is between that of conductors (e.g., copper) and insulators (e.g., soda-lime-silicon glass). The methods disclosed herein can be used, for example, to form a complementary metal oxide semiconductor (CMOS) device or a portion of such a device. However, unless otherwise specified, the present disclosure is not necessarily limited to these examples.

[0108] As used herein, the term "dipole layer" in a semiconductor structure refers to a region where a net dipole moment is established at or near the surface or interface of a semiconductor material. It is formed by introducing (e.g., depositing) a different material (usually a dielectric) on a surface or interface. A dielectric is an electrical insulator that can be polarized by an applied electric field. Additionally or alternatively, the dielectric surface may include a high-κ dielectric surface (i.e., having a high dielectric constant compared to silicon oxide). The dipole layer is generated by charge redistribution (i.e., polarization), resulting in positive charge accumulation on one side and negative charge accumulation on the other side. The polarizability of the dipole layer has a significant effect on the semiconductor structure, such as changing surface properties, increasing carrier lifetime, generating energy barriers, and controlling band alignment. Dipole layers are widely used in semiconductor technology to enhance device performance and achieve specific functions by manipulating surface and interface properties.

[0109] In some embodiments, the methods disclosed herein are used to form semiconductor devices used as field effect transistors (FETs). One of the most common FETs in digital circuits is the metal oxide semiconductor field effect transistor (MOSFET). A MOSFET is a device having source, gate, and drain terminals that can control the flow of current by applying a voltage to the gate, thereby changing the conductivity between the drain and source. Thus, depending on the applied voltage, the semiconductor device can be used to amplify or switch (e.g., on / off) an electrical signal. The minimum voltage required to create / terminate a conductive path or channel between the drain and source is often referred to as the threshold voltage (V t ).

[0110] Typically, semiconductors include metal oxides and / or oxide contaminants and a relatively thin equivalent oxide thickness (e.g., 1 nm). The methods disclosed herein allow the formation of semiconductor devices characterized by low EOT and particularly controlled, for example, higher or lower threshold voltages. Thus, the resulting semiconductors provide transistors such as MOSFETs with lower leakage currents and increased electrical performance. The methods are useful for producing semiconductors with different threshold voltages (V t ) (e.g., lower and / or higher) to optimize response rate and power consumption. For example, the gate voltage that creates a conductive channel between the source and drain of an n-MOSFET can be increased. For example, the n-MOSFET can be included in a CMOS-based integrated circuit. Additionally or alternatively, the gate voltage that creates a conductive channel between the source and drain of a p-MOSFET can be reduced. For example, the p-MOSFET can be included in a CMOS-based integrated circuit. In other words, the present method is particularly useful for increasing or reducing the voltage at which an n-MOSFET switches from an off state to an on state, and reducing or increasing the voltage at which a p-MOSFET switches from an off state to an on state.

[0111] Specifically, forming a film (e.g., a metal nitride film) or layer comprising metal and nitrogen on a substrate as described herein involves a cyclic deposition process, such as an atomic layer deposition process or a cyclic chemical vapor deposition process. In some embodiments, the cyclic deposition process includes one or more cycles. In certain embodiments, the method disclosed herein includes at least 1 cycle, at least 2 cycles, at least 5 cycles, at least 10 cycles, at least 20 cycles, at least 40 cycles, at least 100 cycles, at least 200 cycles, at least 400 cycles, at least 600 cycles, at least 1000 cycles. In some embodiments, these steps may be repeated for at least 1 cycle to at most 1000 cycles, or at least 2 cycles to at most 100 cycles, or at least 5 cycles to at most 50 cycles.

[0112] A cycle includes two or more pulses. In some embodiments, at least one pulse involves a self-limiting surface reaction. In some embodiments, all pulses involve a self-limiting surface reaction. In some embodiments, the cycle includes a metal precursor pulse and a nitrogen reactant (reactant) pulse. With a metal precursor pulse, one or more metal precursors are provided to a reaction chamber. With a nitrogen reactant pulse, a nitrogen reactant is provided to a reaction chamber. Thus, a thin film is formed on at least a portion of a substrate comprising metal and nitrogen (e.g., a metal nitride). In some embodiments, the metal precursor pulse precedes the nitrogen reactant pulse. Nevertheless, in other embodiments, the nitrogen reactant pulse may precede the metal precursor pulse.

[0113] It should be understood that any two steps and / or pulses can be separated by a purge. Thus, in some embodiments, the step of contacting one or more metal precursors and the step of providing a nitrogen reactant are separated by a purge. In some embodiments, subsequent cycles are separated by a purge.

[0114] In certain embodiments, the methods disclosed herein provide one or more cycles comprising the steps of contacting one or more metal precursors with at least a portion of a substrate and providing a nitrogen reactant into a reaction chamber, the cycles being quasi oxygen-free, and preferably completely oxygen-free. More specifically, the disclosed methods provide deposition of metal and nitrogen-containing films without oxygen contaminants, thereby reducing the dipole equivalent oxide thickness (EOT) and the amount of deposition defects.

[0115] In some embodiments, the substrate can be made of semiconductor materials, including, for example, silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide. In some preferred embodiments, the substrate includes silicon or silicon oxide. In a specific embodiment, the substrate is made of silicon or silicon oxide.

[0116] In certain embodiments, the substrate includes at least one of an interlayer and a high-k layer, wherein the method disclosed herein further includes the step of annealing the substrate, thereby forming a dipole layer. The interlayer referred to herein can be made of a semiconductor material, including, for example, silicon, silicon oxide, and silicate. The interlayer is typically formed between the silicon substrate and the high-k layer. The high-κ layer includes a high-κ dielectric having a dielectric constant greater than the dielectric constant of silicon oxide, for example, greater than about 7. Non-limiting exemplary high-κ dielectrics include hafnium oxide (HfO2), tantalum oxide (Ta2O5), zirconium oxide (ZrO2), titanium oxide (TiO2), hafnium silicate (HfSiO x ), aluminum oxide (Al2O3) or lanthanum oxide (La2O3), mixtures thereof and stacks thereof.

[0117] In some embodiments, the methods disclosed herein provide for forming a film containing metal and nitrogen on an interlayer. In some embodiments, the methods disclosed herein provide for forming a film containing metal and nitrogen on a high-k layer.

[0118] The continuous substrate may extend beyond the boundaries of the processing / reaction chamber in which the deposition process occurs. In some processes, the continuous substrate may be moved through the processing chamber so that the process continues until the end of the substrate is reached. The continuous substrate may be provided from a continuous substrate feed system to allow the continuous substrate to be manufactured and output in any suitable form.

[0119] Non-limiting examples of a continuous substrate may include a sheet or a flexible material. A continuous substrate may also include a carrier or sheet on which a non-continuous substrate is mounted.

[0120] In a particular embodiment, the method disclosed herein provides one or more cycles including the following steps: providing an oxygen reactant into a reaction chamber, thereby forming a film containing metal, oxygen and nitrogen on at least a portion of the substrate. In other words, the present disclosure may alternatively or additionally provide for intentionally introducing an oxygen reactant during one or more cycles of the method disclosed herein. Therefore, the one or more cycles generated include three or more pulses. In some embodiments, the cycle includes a metal precursor pulse, a nitrogen reactant pulse and an oxygen reactant pulse. Therefore, a thin film is formed on at least a portion of a substrate containing metal, nitrogen and oxygen (e.g., metal oxynitride). In some embodiments, the metal precursor pulse precedes the nitrogen reactant pulse and the oxygen reactant pulse. Nevertheless, in other embodiments, the nitrogen reactant pulse and the oxygen reactant pulse may be before the metal precursor pulse. Nevertheless, in other embodiments, the nitrogen reactant pulse may be before the metal precursor pulse and the oxygen reactant pulse. The technician understands that different pulse sequences are possible. Advantageously, by controlling the amount of oxygen and / or oxygen contaminants during each deposition cycle, the present disclosure can reduce the amount of surface defects during dipole layer deposition, and control the EOT to have a well-defined film of desired thickness without reducing conductivity and / or capacitance. Furthermore, films containing metals, oxygen, and nitrogen provide additional flexibility because films containing reactive oxides can be used for subsequent reactions or deposition of materials.

[0121] In certain embodiments, suitable oxidants include oxygen reactants or gases. In preferred embodiments, the oxygen reactant is selected from the group consisting of at least one of H2O, D2O, H2O2, O3, O2, N2O, NO, N2O5, SO2, oxygen-containing plasmas, and oxygen radicals.

[0122] As used herein, the term "deposition" or "cyclic deposition" or "cyclic deposition process" or "cyclic deposition process" refers to the sequential introduction of metal precursors (and / or reactants) into a reaction chamber to deposit a layer or film on a substrate, and includes processing techniques such as atomic layer deposition (ALD), cyclic chemical vapor deposition (cyclic CVD), and hybrid cyclic deposition processes including an ALD component and a cyclic CVD component. In a preferred embodiment, the deposition process disclosed herein refers to an atomic layer deposition process. Typically, one deposition cycle can form a film or layer of about 0.10 nm. However, the experimental thickness can vary depending on the amount and type of cycles and the available reaction sites on the substrate. In a preferred embodiment, the method disclosed herein provides an average thickness of the dipole layer of 1 nm or less, or 0.75 nm or less, preferably 0.50 nm or less, or 0.4 nm or less, or 0.3 nm or less, preferably 0.25 nm or less, or 0.2 nm or less, more preferably 0.10 nm or less. In some embodiments, the dipole layer is grown at a rate of 0.10 nm or less per alternating precursor / reactive gas and purge gas (eg, inert carrier gas) pulses. For many electronic applications, including work function and / or threshold voltage adjustment in transistors, lower thickness layers may be desirable.

[0123] The term "atomic layer deposition" (ALD) refers to a vapor deposition process in which a deposition cycle (usually multiple consecutive deposition cycles) is performed in a process chamber. The term atomic layer deposition as used herein is also meant to include processes designated by related terms such as chemical vapor atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, organometallic MBE, and chemical beam epitaxy when performed with alternating pulses of precursor / reactive gas and purge gas (e.g., inert carrier gas).

[0124] Typically, for an ALD process, during each cycle, a (metal) precursor is introduced into a reaction chamber and chemically adsorbed onto a deposition surface (e.g., a substrate surface that may include previously deposited material or other material from a previous ALD cycle) and forms a material, such as approximately a monolayer or sub-monolayer of material, or several monolayers of material, or multiple monolayers of material, that is not susceptible to reaction with additional precursors (i.e., a self-limiting reaction). Thereafter, in some cases, a reactant (e.g., another precursor or a reactive gas) may subsequently be introduced into the process chamber for converting the chemically adsorbed precursor into the desired material on the deposition surface. The reactant is capable of further reacting with the precursor. During one or more repetitions, such as during each deposition step, a purge step may be utilized to remove any excess precursor from the process chamber and / or any excess reactant and / or reaction byproducts from the reaction chamber. Note that, as used herein, an ALD process does not necessarily include a series of self-limiting surface reactions. Advantageously, the method disclosed herein allows the formation of a dipole layer that does not require full film closure to work. Thus, faster deposition is allowed with greater error tolerance than disclosed in the prior art.

[0125] In some embodiments, the plurality of deposition cycles may include a plurality of main cycles. The main cycle may include an oxygen reactant pulse and one or more sub-cycles. The sub-cycle includes a nitrogen reactant pulse followed by a metal precursor pulse. Thus, in some embodiments, the plurality of deposition cycles may be represented by formula i):

[0126] [(nitrogen reactant + metal precursor) x sub-cycle + oxygen reactant] x main cycle i)

[0127] Wherein, "nitrogen reactant" represents a nitrogen reactant pulse, "metal precursor" represents a metal precursor pulse, "x subcycle" represents the number of subcycles / main cycle, "oxygen reactant" represents an oxygen reactant pulse, "x main cycle" represents the number of main cycles, and "+" represents that one pulse occurs after the other. In such an embodiment, the oxygen reactant is introduced only during the oxygen reactant pulse, so that oxygen-related defects are minimized.

[0128] Additionally or alternatively, in some embodiments, a pulse of a metal precursor precedes a pulse of a nitrogen reactant, resulting in a cyclic deposition process that can be described by equation ii):

[0129] [(metal precursor + nitrogen reactant) x sub-cycle + oxygen reactant] x main cycle ii)

[0130] In some embodiments, a metal precursor pulse may be performed before performing the main cycle, as shown in equation iii):

[0131] [Metal Precursor + [(Nitrogen Reactant + Metal Precursor) x Sub-cycle + Oxygen Reactant] x Main Cycle iii)

[0132] In some embodiments, the method comprises from at least 2 sub-cycles to at most 5 sub-cycles, or from at least 5 sub-cycles to at most 10 sub-cycles, or from at least 10 sub-cycles to at most 20 sub-cycles, or from at least 20 sub-cycles to at most 50 sub-cycles, or from at least 50 sub-cycles to at most 100 sub-cycles, or from at least 100 sub-cycles to at most 200 sub-cycles, or from at least 200 sub-cycles to at most 500 sub-cycles, or from at least 500 sub-cycles to at most 1000 sub-cycles, or from at least 1000 sub-cycles to at most 2000 sub-cycles.

[0133] In certain embodiments, the methods disclosed herein provide a cycle comprising one or more metal precursor pulses and one or more nitrogen reactant pulses. In some preferred embodiments, each pulse is followed by a purge of an inert gas selected from at least one of N2 and a noble gas.

[0134] In some embodiments, the metal precursor pulse lasts from at least 0.01 second to at most 120 seconds, or from at least 0.01 second to at most 0.1 second, or from at least 0.01 second to at most 0.02 seconds, or from at least 0.02 seconds to at most 0.05 seconds, or from at least 0.05 seconds to at most 0.1 second, or from at least 0.1 second to at most 20 seconds, or from at least 0.1 second to at most 0.2 seconds, or from at least 0.2 seconds to at most 0.5 seconds, or from at least 0.5 seconds to at most 1.0 second, or from at least 1.0 second to at most 2.0 seconds, or from at least 2.0 seconds to at most 5.0 seconds, or from at least 5.0 seconds to at most 10.0 seconds, or from at least 10.0 seconds to at most 20.0 seconds. In some embodiments, the nitrogen reactant pulse and / or the oxygen reactant pulse lasts at least 0.1 second to at most 20 seconds, or at least 0.1 second to at most 0.2 seconds, or at least 0.2 seconds to at most 0.5 seconds, or at least 0.5 seconds to at most 1.0 seconds, or at least 1.0 seconds to at most 2.0 seconds, or at least 2.0 seconds to at most 5.0 seconds, or at least 5.0 seconds to at most 10.0 seconds, or at least 10.0 seconds to at most 20.0 seconds, or at least 20.0 seconds to at most 120.0 seconds, or at least 20.0 seconds to at most 50.0 seconds, or at least 50.0 seconds to at most 80.0 seconds, or at least 80.0 seconds to at most 120.0 seconds.

[0135] In certain embodiments, the methods disclosed herein provide that one or more metal precursors include an element selected from the group consisting of Mg, Ca, Sr, Ba, Al, Ga, In, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Re, Ge, Sb, Zn, and W. The metal element can be in any suitable oxidation state, such as oxidation state +2, oxidation state +3, oxidation state +4, oxidation state +5, or oxidation state +6. The metal precursor can have a low carbon impurity content, such as a carbon content of 1.0 or 0.1 atomic % or less. One or more metal precursors can include a ligand. The ligand is typically an ion or molecule having a functional group that can bind to a central metal atom to form a coordination complex. In some embodiments, the methods disclosed herein provide that the ligand is selected from the group consisting of at least one of an amine, an alkenyl, a carbonyl, an alkoxide, a β-diketone, a diazadiene, an amidine, a halogen, a guanidinium salt, a triazene compound, a carboxylate, a cyclopentadienyl, and / or an aryl group.

[0136] In certain embodiments, the methods disclosed herein provide that one or more metal precursors include a metal element selected from the group consisting of at least one of Ga and W. The inventors surprisingly found that films containing nitrogen, gallium and / or tungsten are particularly advantageous for controlling the threshold voltage of semiconductor structures.

[0137] In certain embodiments, the methods disclosed herein provide that the metal element is tungsten (W), and the one or more metal precursors are selected from the group consisting of at least one of formula (I), formula (II) and formula (III), wherein,

[0138]

[0139] Q 1 ,Q 2 ,Q 3 ,Q 4 ,Q 5 ,Q 6 Each independently selected from CO, F, Cl, Br, I, alkyl, alkenyl, N(R 1 )2, alkoxy, cycloalkoxy, cycloalkyl, aryl, arylalkyl, alkylaryl, cyclopentadienyl, alkyl-substituted cyclopentadienyl, and heteroalkyl; wherein each R 1 are independently selected from hydrogen, alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, and heteroalkyl.

[0140] In some embodiments, the present disclosure provides Q 1 ,Q 2 ,Q 3 ,Q 4 ,Q 5 ,Q6 Each independently selected from CO, F, Cl, Br, I, C 1-20 Alkyl, C 2-20 Alkenyl, N(R 1 2. C 1-20 Alkoxy, C 3-20 Cycloalkoxy, C 3-20 Cycloalkyl, C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkyl C 6-20 Aryl, cyclopentadienyl, C 1-20 Alkyl substituted cyclopentadienyl and heterocyclic C 1-20 Alkyl. Where each R 1 are independently selected from hydrogen, C 1-20 Alkyl, C 3-20 Cycloalkyl, C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkyl C 6-20 Aryl and heterocyclic C 1-20 alkyl.

[0141] In some embodiments, the present disclosure provides Q 1 ,Q 2 ,Q 3 ,Q 4 ,Q 5 ,Q 6 Each independently selected from CO, F, Cl, Br, I, C 1-8 Alkyl, C 2-8 Alkenyl, N(R 1 2. C 1-8 Alkoxy, C 3-8 Cycloalkoxy, C 3-8 Cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, C 1-8 Alkyl C 6-10 Aryl, cyclopentadienyl, C 1-8 Alkyl substituted cyclopentadienyl and heterocyclic C 1-8 Alkyl; wherein each R 1 are independently selected from hydrogen, C 1-8 Alkyl, C 3-8 Cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, C 1-8 Alkyl C 6-10 Aryl and heterocyclic C 1-8 alkyl.

[0142] In some embodiments, the present disclosure provides Q 1 ,Q 2 ,Q 3 ,Q 4 ,Q 5 ,Q 6 Each independently selected from CO, F, Cl, Br, I, C 1-4 Alkyl, C 2-4 Alkenyl, N(R 1 2. C 1-4 Alkoxy, C 3-8 Cycloalkoxy, C 3-8 Cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-4 Alkyl, C 1-4 Alkyl C 6-10 Aryl, cyclopentadienyl, C 1-4 Alkyl substituted cyclopentadienyl and heterocyclic C 1-4 Alkyl; wherein each R 1 are independently selected from hydrogen, C 1-4 Alkyl, C 3-8 Cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-4 Alkyl, C 1-4 Alkyl C 6-10 Aryl and heterocyclic C 1-4 alkyl.

[0143] In certain embodiments, the methods disclosed herein provide that the metal element is tungsten (W), and the one or more metal precursors are selected from WF6, WCl6, WBr6, WI6, W(CO)6, WF2(CO)4, WCl2(CO)4, WBr2(CO)4, W(Me)6, W(Et)6, W(nPr)6, W(nBu)6, W(tBu)6, W(NME2)6, W(NtBu)2(NMe2)4, W(NEt2)6, W(acac)2( CO)4,W(acac)1(CO)5,W(acac)3(CO)3,W(Pyr)6,W(benzene)(CO)5,W(toluene)(CO)5,W(cyclopentadienyl)(CO)5,W(naphthalene)(CO)5,WF5,WCl5,WBr5,WI5,W(CO)5,WF2(CO)3,WCl2(CO)3,WBr2(CO)3,W(Me)5,W(Et)5,W(nPr)5,W(nBu)5,W(tBu) 5,W(NME2)5,W(NtBu)2(NMe2)3,W(NEt2)5,W(acac)2(CO)3,W(acac)1(CO)4,W(acac)3(CO)2,W(Pyr)5,W(benzene)(CO)4,W(toluene)(CO)4,W(cyclopentadienyl)(CO)4,W(naphthalene)(CO)4,WF4,WCl4,WBr4,WI4,W(CO)4,WF2(CO)2,WCl2(CO)2,W Br2(CO)2, W(Me)4, W(Et)4, W(nPr)4, W(nBu)4, W(tBu)4, W(NME2)4, W(NtBu)2(NMe2)2, W(NEt2)4, W(acac)2(CO)2, W(acac)1(CO)3, W(acac)3(CO)1, W(Pyr)4, W(benzene)(CO)3, W(toluene)(CO)3, W(cyclopentadienyl)(CO)3 and W(naphthalene)(CO)3.

[0144] In certain embodiments, the methods disclosed herein provide that the metal element is gallium (Ga), and the one or more metal precursors are selected from the group of formula (IV), wherein,

[0145]

[0146] Q 7 ,Q 8 ,Q 9 Each independently selected from F, Cl, Br, I, alkyl, alkenyl, N(R 2 )2, alkoxy, cycloalkoxy, cycloalkyl, aryl, arylalkyl, alkylaryl, R 3 NC(R 4 )NR5 , R 6 NC[N(R 7 )2]NR 8 , R 9 N3R 10 , cyclopentadienyl, alkyl-substituted cyclopentadienyl, and heteroalkyl; wherein each R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,R 10 are independently selected from hydrogen, alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, and heteroalkyl.

[0147] In some embodiments, the present disclosure provides Q 7 ,Q 8 ,Q 9 Each independently selected from F, Cl, Br, I, C 1-20 Alkyl, C 2-20 Alkenyl, N(R 2 2. C 1-20 Alkoxy, C 3-20 Cycloalkoxy, C 3-20 Cycloalkyl, C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkyl C 6-20 Aryl, R 3 NC(R 4 )NR 5 , R 6 NC[N(R 7 )2]NR 8 , R 9 N3R 10 , cyclopentadienyl, C 1-20 Alkyl substituted cyclopentadienyl and heterocyclic C 1-20 Alkyl; wherein each R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,R 10 are independently selected from hydrogen, C 1-20 Alkyl, C 3-20 Cycloalkyl, C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, C 1-20Alkyl C 6-20 Aryl and heterocyclic C 1-20 alkyl.

[0148] In some embodiments, the present disclosure provides Q 7 ,Q 8 ,Q 9 Each independently selected from F, Cl, Br, I, C 1-8 Alkyl, C 2-8 Alkenyl, N(R 2 2. C 1-8 Alkoxy, C 3-8 Cycloalkoxy, C 3-8 Cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, C 1-8 Alkyl C 6-10 Aryl, R 3 NC(R 4 )NR 5 , R 6 NC[N(R 7 )2]NR 8 , R 9 N3R 10 , cyclopentadienyl, C 1-8 Alkyl substituted cyclopentadienyl and heterocyclic C 1-8 Alkyl; wherein each R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,R 10 are independently selected from hydrogen, C 1-8 Alkyl, C 3-8 Cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, C 1-8 Alkyl C 6-10 Aryl and heterocyclic C 1-8 alkyl.

[0149] In some embodiments, the present disclosure provides Q 7 ,Q 8 ,Q 9 Each independently selected from F, Cl, Br, I, C 1-4 Alkyl, C 2-4 Alkenyl, N(R 2 2. C 1-4 Alkoxy, C 3-8 Cycloalkoxy, C 3-8Cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-4 Alkyl, C 1-4 Alkyl C 6-10 Aryl, R 3 NC(R 4 )NR 5 , R 6 NC[N(R 7 )2]NR 8 , R 9 N3R 10 and cyclopentadienyl, C 1-4 Alkyl substituted cyclopentadienyl, heterocyclic C 1-4 Alkyl; wherein each R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,R 10 are independently selected from hydrogen, C 1-4 Alkyl, C3-8 cycloalkyl, C 6-10 Aryl, C 6-10 Aryl C 1-4 Alkyl, C 1-4 Alkyl C 6-10 Aryl and heterocyclic C 1-4 alkyl.

[0150] In a specific embodiment, the method disclosed herein provides that the metal element is gallium (Ga), and one or more metal precursors are selected from GaF3, GaCl3, GaBr3, GaI3, Ga(Me)3, Ga(Et)3, Ga(nPr)3, Ga(nBu)3, Ga(tBu)3, Ga(NMe2)3, Ga(NtBu)2(NMe2)1, Ga(NtBu)1(NMe2)2, Ga(NEt2)3, Ga(Pyr)3, Ga(guanidine)3 and Ga(triazene)3.

[0151] In certain embodiments, the methods disclosed herein provide that the nitrogen reactant is selected from N(R 11 )3 and (R 12 )NN(R 13 ), where each R 11 ,R 12 ,R 13 independently selected from hydrogen, alkyl, alkenyl, cycloalkyl and Si(R 14 )3; where R 14 is selected from alkyl, alkenyl, alkoxy and Si(R 15 )3; and wherein R15 Selected from alkyl, alkenyl and alkoxy.

[0152] In some embodiments, the present disclosure provides that each R 11 ,R 12 ,R 13 are independently selected from hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, Ring C 3-20 Alkyl and Si(R 14 )3, where R 14 Selected from C 1-20 Alkyl, C 2-20 Alkenyl, C 1-20 Alkoxy and Si(R 15 )3; and wherein R 15 Selected from C 1-20 Alkyl, C 1-20 Alkenyl, C 1-20 Alkoxy.

[0153] In some embodiments, the present disclosure provides that each R 11 ,R 12 ,R 13 are independently selected from hydrogen, C 1-8 Alkyl, C 2-8 Alkenyl, Ring C 3-8 Alkyl and Si(R 14 )3, where R 14 Selected from C 1-8 Alkyl, C 2-8 Alkenyl, C 1-8 Alkoxy and Si(R 15 )3; and wherein R 15 Selected from C 1-8 Alkyl, C 2-8 Alkenyl and C 1-8 Alkoxy.

[0154] In some embodiments, the present disclosure provides that each R 11 ,R 12 ,R 13 are independently selected from hydrogen, C 1-4 Alkyl, C 2-4 Alkenyl, Ring C 3-8 Alkyl and Si(R 14 )3, where R 14 Selected from C 1-4 Alkyl, C 2-4 Alkenyl, C 1-4 Alkoxy and Si(R 15 )3; and wherein R 15 Selected from C 1-4 Alkyl, C 2-4 Alkenyl and C 1-4Alkoxy.

[0155] In certain embodiments, the methods disclosed herein provide that one or more metal precursors are metal bis(arene) precursors, wherein the arene ligand is η6-benzene or an η6-benzene derivative.

[0156] In certain embodiments, the methods disclosed herein provide a nitrogen reactant selected from the group including at least one of: NH3, diazene (N2H2), hydrazine (N2H4), methylhydrazine (N2MeH3), ethylhydrazine (N2EtH3), propylhydrazine (N2nPrH3), butylhydrazine (N2nBuH3), tert-butylhydrazine (N2tBuH3), 1,1-dimethylhydrazine (N2Me2H2), 1,1-diethylhydrazine (N2Et2H2), 1,1-dipropylhydrazine (N2nPr2H2), 1,1-dibutylhydrazine (N2nBu2H2), trimethylsilylhydrazine (N2[Si(Me)3]H2) and tris(trimethylsilyl)silylhydrazine (N2[Si(Si(Me)3)3]H2). Advantageously, the nitrogen reactants disclosed herein are characterized by low volatility and are therefore easily evaporated. Thus, the methods disclosed herein do not necessarily have to be performed at elevated temperatures (eg, near the decomposition temperature of the disclosed materials).

[0157] In some specific embodiments, the methods disclosed herein provide that the metal and nitrogen-containing film includes at least one of gallium nitride (GaN) and tungsten nitride (WN). Advantageously, gallium nitride (GaN) and tungsten nitride (WN) are particularly suitable components of the p-type dipole layer. Advantageously, gallium nitride (GaN) and tungsten nitride (WN) are particularly suitable components of the n-type dipole layer. In addition, the inventors have found that the film or layer containing GaN and / or WN deposited by the methods disclosed herein is resistant to chemicals such as acids and bases, oxidation and heat. Therefore, the methods disclosed herein provide semiconductor structures with high functional density while overcoming at least some of the disadvantages of the prior art.

[0158] In certain embodiments, the methods disclosed herein provide that the metal, oxygen, and nitrogen containing film includes at least one of gallium oxynitride (GaON) and tungsten oxynitride (WON).

[0159] It should be understood that when a film or layer containing metal nitrides and / or metal oxynitrides is deposited on a substrate, a certain degree of mixing of the constituents of these layers may occur. For example, when a layer containing gallium oxynitride (GaON) is deposited on a tungsten nitride (WN) layer, at least one of gallium, nitrogen, or oxygen may be incorporated into the layer containing tungsten nitride, such as by diffusion, surface isolation, or another process. For example, when a layer containing tungsten oxynitride (WON) is deposited on hafnium oxide (HfO2), hafnium may be incorporated into the layer containing tungsten nitride. In some embodiments, such mixing may result in the formation of a sandwich containing both components in each layer. In addition, extremely thin metal nitride and / or metal oxynitride films may further contain hydrogen and / or carbon in the resulting deposited film or layer.

[0160] It should be understood that when a metal nitride is abbreviated by a chemical formula, the chemical formula may represent the metal nitride in a given stoichiometry, or any other stoichiometry, including non-stoichiometric forms, depending on, for example, the oxidation state of the metal in question. For example, when tungsten nitride is abbreviated as "WN", the term "WN" may refer to a tungsten and nitrogen-containing material, wherein the tungsten and nitrogen are present in a 1:1 ratio, or in any other suitable ratio, such as 0.8:2, 1:2, 1.5:2, 0.8:1, 0.9:1, 0.95:1, 1:1.05, 1:1.1, 1.2, 1.5, 2:1, 2.5:1, etc. Similar considerations apply to the metal oxynitrides disclosed herein.

[0161] In certain embodiments, the methods disclosed herein provide for contacting a ligand compound with at least a portion of a substrate together with one or more metal precursors. In other words, additional ligands may be added to the reaction chamber to increase the efficiency of film formation or material deposition. In some embodiments, the ligands may interact with the substrate surface to inhibit or promote chemical adsorption of the metal precursor to the surface. In some embodiments, the ligands may interact with nitrogen reactants to increase the reaction rate between the chemically adsorbed metal and nitrogen reactants. In some embodiments, the ligands may interact with active surface sites on the substrate to reduce or inactivate the activity of those surface sites, i.e., poison them.

[0162] In some preferred embodiments, the methods disclosed herein provide a ligand compound selected from the group consisting of XN(R 16 )2 and at least one of β-diketone; wherein X is hydrogen or an alkali metal selected from Li, Na, K and Rb; and wherein R 16 Selected from alkyl and Si(R 17 )3; and wherein R 17 Selected from alkyl, alkenyl and alkoxy.

[0163] In some embodiments, the present disclosure provides R 16 Selected from C 1-8Alkyl and Si(R 17 )3; and wherein R 17 Selected from C 1-8 Alkyl, C 2-8 Alkenyl and C 1-8 Alkoxy.

[0164] In some embodiments, the present disclosure provides R 16 Selected from C 1-4 Alkyl and Si(R 17 )3; and wherein R 17 Selected from C 1-4 Alkyl, C 2-4 Alkenyl and C 1-4 Alkoxy.

[0165] In some embodiments, the present disclosure provides that the ligand compound is a dialkyldisilazane or a salt thereof. In some embodiments, the present disclosure provides that the ligand compound is selected from acetylacetonate, 2,2,6,6-tetramethylheptane-3,5-dioate and 1,1,1,5,5,5-hexafluoropentane-2,4-dioate.

[0166] In a specific embodiment, preferably, wherein the metal precursor is a metal bis(arene) precursor, the cycle provided by the present disclosure further comprises a step of providing an organic molecule reactant comprising at least one halogen group to the reaction chamber before or after providing the nitrogen reactant. The organic molecule reactant is capable of reacting or interacting with the metal precursor to produce a more reactive metal coordination complex, promoting the reaction with the nitrogen reactant and / or the oxygen reactant.

[0167] In certain embodiments, the methods disclosed herein provide an organic molecule reactant selected from formula (V), wherein,

[0168]

[0169] Q 10 ,Q 11 ,Q 12 ,Q 13 are each independently selected from hydrogen, halogen, alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkoxy, and heteroalkyl; and wherein, Q 10 ,Q 11 ,Q 12 ,Q 13 At least one of them is a halogen.

[0170] In some embodiments, the present disclosure provides Q 10 ,Q 11 ,Q 12 ,Q 13 are each independently selected from hydrogen, halogen, C 1-8 Alkyl, C 1-8Alkenyl, C 3-8 Cycloalkyl, C 6-10 Aryl, C 1-8 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-8 Alkyl, C 1-8 Alkoxy and heterocyclic C 1-8 alkyl; and wherein Q 10 ,Q 11 ,Q 12 ,Q 13 At least one of them is a halogen.

[0171] In some embodiments, the present disclosure provides Q 10 ,Q 11 ,Q 12 ,Q 13 are each independently selected from hydrogen, halogen, C 1-4 Alkyl, C 1-4 Alkenyl, C 3-8 Cycloalkyl, C 6-10 Aryl, C 1-4 Alkyl C 6-10 Aryl, C 6-10 Aryl C 1-4 Alkyl, C 1-4 Alkoxy and heterocyclic C 1-4 alkyl; and wherein Q 10 ,Q 11 ,Q 12 ,Q 13 At least one of is F, Cl, Br or I.

[0172] In certain embodiments, the methods disclosed herein provide that the organic molecule reactant is selected from methyl chloride (CH3Cl), methyl bromide (CH3Br), methyl iodide (CH3I), dichloromethane (CH2Cl2), dibromomethane (CH2Br2), diiodomethane (CH2I2), trichloromethane (CHCl3), tribromomethane (CHBr3), triiodoform (CHI3), ethyl chloride (C2H5Cl), ethyl bromide (C2H5Br), ethyl iodide (C2H5I), 1,2-dichloroethane (C2H4Cl2), 1,2-dibromoethane (C2H4Br2), 1,2-diiodoethane (C2H4I2), propyl chloride (C3H7Cl), , bromopropane (C3H7Br), iodopropane (C3H7I), 1,3-dichloropropane (C3H6Cl2), 1,3-dibromopropane (C3H6Br2), 1,3-diiodopropane (C3H6I2), chlorobutane (C4H9Cl), bromobutane (C4H9Br), iodobutane (C4H9I), 1,4-dichlorobutane (C4H8Cl2), 1,4-dibromobutane (C4H8Br2), 1,4-diiodobutane (C4H8I2), benzyl chloride (C7H7Cl), benzyl bromide (C7H7Br), benzyl iodide (C7H7I), chlorobenzene (C6H5Cl), bromobenzene (C6H5Br) and iodobenzene (C6H5I).

[0173] It should be understood that the following examples can be applied to any of the methods disclosed herein, regardless of the precursors and / or reactants used in those methods, unless the corresponding examples would render the method in question unfeasible.

[0174] In some embodiments, the metal nitride-containing film is deposited at a temperature of at least 100° C. to at most 500° C., or at a temperature of at least 200° C. to at most 450° C., or at a temperature of at least 300° C. to at most 400° C., or at a temperature of at least 350° C. to at most 450° C.

[0175] In some embodiments, the metal precursor is provided to the reaction chamber from a precursor source maintained at a temperature of at least 25°C to at most 200°C, or at least 50°C to at most 150°C, or at least 75°C to at most 125°C.

[0176] In some embodiments, nitrogen reactant is provided to the reaction chamber from a nitrogen source maintained at a temperature of at least 25°C to at most 200°C, or at least 50°C to at most 150°C, or at least 75°C to at most 125°C.

[0177] In some embodiments, oxygen reactant is provided to the reaction chamber from an oxygen source maintained at a temperature of at least 25°C to at most 200°C, or at least 50°C to at most 150°C, or at least 75°C to at most 125°C.

[0178] In some embodiments, the metal and nitrogen containing film is deposited at a pressure of at least 0.01 Torr to at most 100 Torr, or at least 0.1 Torr to at most 50 Torr, or at least 0.5 Torr to at most 25 Torr, or at least 1 Torr to at most 10 Torr, or at least 2 Torr to at most 5 Torr.

[0179] The metal and nitrogen containing film can be deposited in any suitable reactor. Therefore, in some embodiments, the metal and nitrogen containing film is deposited in a cross-flow reactor. In some embodiments, the metal and nitrogen containing film is deposited in a showerhead reactor. In some embodiments, the metal and nitrogen containing film is deposited in a hot wall reactor. In some embodiments, the metal and nitrogen containing film is deposited in a cold wall reactor. Doing so can advantageously improve the uniformity and / or repeatability of the metal and nitrogen containing film deposition process.

[0180] In some embodiments, after the cyclic deposition process, the substrate is subjected to an annealing step in an environment containing hydrogen and nitrogen. Suitably, the annealing step may be performed at a temperature of at least 300° C. to at most 600° C. Alternatively, the annealing step may be performed at a temperature of at least 300° C. to at most 1000° C.

[0181] In some embodiments, the metal precursor is provided to the reaction chamber from a temperature-controlled precursor container. In some embodiments, the temperature-controlled precursor container is configured to cool the precursor. In some embodiments, the temperature-controlled precursor container is configured to heat the precursor. In some embodiments, the temperature-controlled precursor container is maintained at a temperature of at least -50°C to at most 20°C, or at a temperature of at least 20°C to at most 250°C, or at least 100°C to at most 200°C.

[0182] In some embodiments, the metal precursor is provided to the reaction chamber by a carrier gas. Exemplary carrier gases include nitrogen (N2) and noble gases such as He, Ne, Ar, Xe or Kr.

[0183] In certain embodiments, the methods disclosed herein further include the step of forming a high-κ dielectric on the dipole layer. The high-κ dielectric has a dielectric constant greater than the dielectric constant of silicon oxide, for example, greater than about 7. Non-limiting exemplary high-κ dielectrics include hafnium oxide (HfO2), tantalum oxide (Ta2O5), zirconium oxide (ZrO2), titanium oxide (TiO2), hafnium silicate (HfSiO x), aluminum oxide (Al2O3) or lanthanum oxide (La2O3), mixtures thereof, and stacks thereof. The method disclosed herein may further include the step of forming a conductive layer on the high-κ dielectric. The other conductive layer may include a nitride such as silicon nitride, or a metal such as aluminum, copper or cobalt. In some embodiments, the semiconductor structure may include the following series of layers in a given order: SiO2, a grown dipole layer, a high-κ dielectric layer, and a conductive layer.

[0184] In some preferred embodiments, the present disclosure relates to a field effect transistor (FET), comprising:

[0185] Substrate;

[0186] A gate dielectric comprising a high-κ dielectric layer deposited on the substrate surface;

[0187] A dipole layer, comprising a metal nitride film and / or a metal oxynitride film, deposited on the surface of the substrate or the high-κ dielectric layer; wherein,

[0188] The gate dielectric has an equivalent oxide thickness (EOT) of between at least 0.1 nm and at most 10 nm, or between at least 0.1 nm and at most 5 nm, or between at least 0.1 nm and at most 2 nm, or between at least 0.1 nm and at most 1.0 nm.

[0189] In some embodiments, the field effect transistor (FET) disclosed herein has a gate leakage current of at most 0.5pA / μm, or at most 0.4pA / μm, or at most 0.3pA / μm, or at most 0.2pA / μm, preferably at most 0.1pA / μm. In some embodiments, the field effect transistor (FET) disclosed herein has a gate leakage current of at most 0.5aA / μm, or at most 0.4aA / μm, or at most 0.3aA / μm. In some embodiments, the field effect transistor (FET) disclosed herein has a gate leakage current of at most 0.5zA / μm, or at most 0.4zA / μm, or at most 0.3zA / μm, or at most 0.2zA / μm, preferably at most 0.1zA / μm. Advantageously, in contrast to that disclosed in the prior art, the field effect transistor (FET) disclosed herein is characterized by low leakage current and fast operation, which leads to energy-saving electronic devices with high performance.

[0190] Preferably, the optional high-κ dielectric layer deposited on the substrate surface is selected from hafnium oxide (HfO2), tantalum oxide (Ta2O5), zirconium oxide (ZrO2), titanium oxide (TiO2), hafnium silicate (HfSiO x ), aluminum oxide (Al2O3) or lanthanum oxide (La2O3) or a mixture thereof.

[0191] In some embodiments, the field effect transistor (FET) disclosed herein may further include a second high-κ dielectric deposited on the dipole layer. In some embodiments, the field effect transistor (FET) disclosed herein may further include a conductive layer deposited on the second high-κ dielectric. Preferably, the other conductive layer may include a nitride, such as silicon nitride, or a metal, such as aluminum, copper or cobalt.

[0192] In some preferred embodiments, the present disclosure relates to a system, wherein the system is configured to perform the methods disclosed herein. Figure 5 A system 500 according to these exemplary embodiments is shown. In the illustrated example, the system 500 includes one or more reaction chambers 502, a metal precursor gas source 504, a nitrogen reactant gas source 506, a purge gas source 508, an exhaust 510, and a controller 512. The reaction chamber 502 can include any suitable reaction chamber, such as an ALD or CVD reaction chamber. Optionally, the system 500 includes additional gas sources, such as an optional oxygen-containing reactant gas source 505.

[0193] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various processes, systems and configurations, and other features, functions, acts and / or properties disclosed herein, and any and all equivalents thereof.

[0194] As an exemplary embodiment, the method disclosed herein can use the method described herein according to Figure 5 According to this embodiment, the metal precursor pulse may include GaMe3 and the nitrogen reactant pulse may include NH3. During the material deposition in the system 500, the following preferred parameters may be used:

[0195] - Substrate temperature: 160°C

[0196] -Pressure in reaction chamber: 8 Torr

[0197] -Metal precursor pulse (GaMe3): 100-150 ms

[0198] - Purge time after metal precursor pulse: 40000 ms

[0199] - Nitrogen reactant pulse (NH3): 10000 ms

[0200] - Purge time after nitrogen reactant pulse: 40000 ms

[0201] - Cycle times: 400 times

[0202] like Figure 6 As shown, the formed GaN film cannot be etched by TiCl4 or NH3 treatment.

[0203] The illustrations presented herein are not meant to be actual views of any particular material, structure, or device but are merely idealized representations used to describe embodiments of the present disclosure.

[0204] The specific embodiments shown and described are illustrative of the present disclosure and its best mode and are not intended to limit the scope of these aspects and embodiments in any way. In fact, for the sake of brevity, the traditional manufacturing, connection, preparation and other functional aspects of the system may not be described in detail. In addition, the connecting lines shown in the various figures are intended to represent exemplary functional relationships and / or physical connections between various elements. In actual systems, there may be many alternative or additional functional relationships or physical connections, and / or may not exist in some embodiments.

[0205] It should be understood that the configuration and / or method described herein are exemplary in nature, and these specific embodiments or examples should not be considered restrictive, because many variations are possible. The specific routine or method described herein can represent one or more of any number of processing strategies. Therefore, the various actions shown can be performed in the order shown, in other orders, or omitted in some cases.

Claims

1. A method for forming a semiconductor structure including a dipole layer, the method comprising the following steps: a) providing a substrate to a reaction chamber; b) executing one or more loops, the loops comprising: i. contacting one or more metal precursors with at least a portion of the substrate by introducing one or more metal precursors into the reaction chamber; and ii. providing a nitrogen reactant into the reaction chamber; A film containing metal and nitrogen is thereby formed on at least a portion of the substrate.

2. The method according to claim 1, wherein: The substrate comprises at least one of an interlayer and a high-k layer, wherein the method further comprises the step of annealing the substrate to form a dipole layer.

3. The method according to claim 1, wherein: The cycle further includes the step of providing an oxygen reactant into the reaction chamber to form a film containing metal, oxygen, and nitrogen on at least a portion of the substrate.

4. The method according to claim 1, wherein: The one or more metal precursors include elements selected from the group consisting of Mg, Ca, Sr, Ba, Al, Ga, In, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Re, Ge, Sb, Zn and W.

5. The method according to claim 1, wherein: The one or more metal precursors include a ligand selected from the group consisting of amine, alkenyl, carbonyl, alkoxide, β-diketone, diazadiene, amidine, halogen, guanidinium salt, triazene, carboxylate, cyclopentadienyl and / or aryl.

6. The method according to claim 1, wherein: The one or more metal precursors include a metal element selected from the group consisting of at least one of Ga and W.

7. The method according to claim 6, wherein: The metal element is tungsten (W), and the one or more metal precursors are selected from the group consisting of at least one of formula (I), formula (II) and formula (III): Among them, Q 1 ,Q 2 ,Q 3 ,Q 4 ,Q 5 ,Q 6 Each independently selected from CO, F, Cl, Br, I, alkyl, alkenyl, N(R 1 )2, alkoxy, cycloalkoxy, cycloalkyl, aryl, arylalkyl, alkylaryl, cyclopentadienyl, alkyl-substituted cyclopentadienyl, and heteroalkyl; wherein each R 1 are independently selected from hydrogen, alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, and heteroalkyl.

8. The method according to claim 6, wherein: The metal element is tungsten (W), and the one or more metal precursors are selected from WF6, WCl6, WBr6, WI6, W(CO)6, WF2(CO)4, WCl2(CO)4, WBr2(CO)4, W(Me)6, W(Et)6, W(nPr)6, W(nBu)6, W(tBu)6, W(NME2)6, W(NtBu)2(NMe2)4, W(NEt2)6, W(acac)2(CO)4, W(aca c)1(CO)5,W(acac)3(CO)3,W(Pyr)6,W(benzene)(CO)5,W(toluene)(CO)5,W(cyclopentadienyl)(CO)5,W(naphthalene)(CO)5,WF5,WCl5,WBr5,WI5,W(CO)5,WF2(CO)3,WCl2(CO)3,WBr2(CO)3,W(Me)5,W(Et)5,W(nPr)5,W(nBu)5,W(tBu)5,W(NME 2)5,W(NtBu)2(NMe2)3,W(NEt2)5,W(acac)2(CO)3,W(acac)1(CO)4,W(acac)3(CO)2,W(Pyr)5,W(benzene)(CO)4,W(toluene)(CO)4,W(cyclopentadienyl)(CO)4,W(naphthalene)(CO)4,WF4,WCl4,WBr4,WI4,W(CO)4,WF2(CO)2,WCl2(CO)2,WBr2 (CO)2, W(Me)4, W(Et)4, W(nPr)4, W(nBu)4, W(tBu)4, W(NME2)4, W(NtBu)2(NMe2)2, W(NEt2)4, W(acac)2(CO)2, W(acac)1(CO)3, W(acac)3(CO)1, W(Pyr)4, W(benzene)(CO)3, W(toluene)(CO)3, W(cyclopentadienyl)(CO)3 and W(naphthalene)(CO)3.

9. The method according to claim 6, wherein: The metal element is gallium (Ga), and the one or more metal precursors are selected from the group of formula (IV): Among them, Q 7 ,Q 8 ,Q 9 Each independently selected from F, Cl, Br, I, alkyl, alkenyl, N(R 2 )2, alkoxy, cycloalkoxy, cycloalkyl, aryl, arylalkyl, alkylaryl, R 3 NC(R 4 )NR 5 , R 6 NC[N(R 7 )2]NR 8 , R 9 N3R 10 , cyclopentadienyl, alkyl-substituted cyclopentadienyl, and heteroalkyl; wherein each R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,R 10 are independently selected from hydrogen, alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, and heteroalkyl.

10. The method according to claim 6, wherein: The metal element is gallium (Ga), and the one or more metal precursors are selected from GaF3, GaCl3, GaBr3, GaI3, Ga(Me)3, Ga(Et)3, Ga(nPr)3, Ga(nBu)3, Ga(tBu)3, Ga(NMe2)3, Ga(NtBu)2(NMe2)1, Ga(NtBu)1(NMe2)2, Ga(NEt2)3, Ga(Pyr)3, Ga(guanidine)3 and Ga(triazene)3.

11. The method according to claim 1, wherein: The nitrogen reactant is selected from N(R 11 )3 and (R 12 )NN(R 13 ), where each R 11 ,R 12 ,R 13 independently selected from hydrogen, alkyl, alkenyl, cycloalkyl and Si(R 14 )3; where R 14 is selected from alkyl, alkenyl, alkoxy and Si(R 15 )3; and wherein R 15 Selected from alkyl, alkenyl and alkoxy.

12. The method according to claim 1, wherein: The nitrogen reactant is selected from the group including at least one of the following: NH3, diazene (N2H2), hydrazine (N2H4), methylhydrazine (N2MeH3), ethylhydrazine (N2EtH3), propylhydrazine (N2nPrH3), butylhydrazine (N2nBuH3), tert-butylhydrazine (N2tBuH3), 1,1-dimethylhydrazine (N2Me2H2), 1,1-diethylhydrazine (N2Et2H2), 1,1-dipropylhydrazine (N2nPr2H2), 1,1-dibutylhydrazine (N2nBu2H2), trimethylsilylhydrazine (N2[Si(Me)3]H2) and tris(trimethylsilyl)silylhydrazine (N2[Si(Si(Me)3)3]H2).

13. The method according to claim 3, wherein: The oxygen reactant is selected from the group consisting of at least one of H2O, D2O, H2O2, O3, O2, N2O, NO, N2O5, SO2, oxygen-containing plasma, and oxygen radicals.

14. The method according to claim 1, wherein: The metal and nitrogen containing film includes at least one of gallium nitride (GaN) and tungsten nitride (WN).

15. The method according to claim 3, wherein: The metal, oxygen, and nitrogen containing film includes at least one of gallium oxynitride (GaON) and tungsten oxynitride (WON).

16. The method according to claim 1, wherein: The ligand compound is selected from the group consisting of XN(R 16 )2 and at least one of β-diketone; wherein X is hydrogen or an alkali metal selected from Li, Na, K and Rb; and wherein R 16 Selected from alkyl and Si(R 17 )3; and wherein R 17 Selected from alkyl, alkenyl and alkoxy.

17. The method according to claim 1, wherein: The ligand compound is a dialkyldisilazane or a salt thereof.

18. The method according to claim 1, wherein: The ligand compound is selected from acetylacetonate, 2,2,6,6-tetramethylheptane-3,5-dioate and 1,1,1,5,5,5-hexafluoropentane-2,4-dioate.

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