Method of selective deposition of triazolylidenes on metallic surfaces

Abstract

A method of selective deposition that includes disposing in a deposition chamber a substrate having metallic and dielectric surfaces. The deposition chamber is connected to a bubbler that contains a 1,2,3-triazolium salt and / or a carboxylate zwitterion form of the 1,2,3-triazole, which are precursors to free 1,2,3-triazol-5-ylidene. By heating the bubbler, gaseous free 1,2,3-triazol-5-ylidene was generated which moved into the deposition chamber, where the 1,2,3-triazol-5-ylidene selectively chemisorbed onto the metallic surface(s).

Description

[0001] METHOD OF SELECTIVE DEPOSITION OF TRIAZOLYLIDENES ON METALLIC SURFACES

[0002] RELATED APPLICATION

[0003] This application claims the benefit of the filing date of United States Application No.

[0004] 63 / 719,463, filed on November 12, 2024, the contents of which are incorporated herein by reference in their entirety.

[0005] FIELD

[0006] The present application pertains to the field of vapour phase and solution phase deposition.

[0007] BACKGROUND

[0008] Self-assembled monolayers (SAMs) on metals have potential applications in sensing, electrochemistry, drug delivery, surface protection, microelectronics and microelectromechanical systems. SAMs of carbon-based ligands known as M-heterocyclic carbenes (NHCs) have been studied (see Crudden, C. M., et al., Nature Chemistry 2014, 6, 409).

[0009] NHCs have played a significant role in the field of transition metal complexes. Unlike most carbenes, which are reactive with limited stability, NHCs typically have one or two heteroatoms adjacent to a carbene carbon. These heteroatoms increase NHCs’ stability such that they can usually be prepared on a gram scale, crystallized or distilled, and stored for long periods of time (e.g., 4 years when stored under N2in a freezer). An Au-NHC bond is estimated to be on an order of 90 kJ / mol stronger than a corresponding Au-phosphine bond, and twice as strong as metal sulfide bonds in molecular complexes (see P. Pyykkd, et al. Chem. Asian J. 1, 623 (2006)). As such, NHCs have potential to be valuable ligands for protecting and functionalizing gold and other metal substrates and / or surfaces.

[0010] Mobile phones, computers and all modern communications infrastructure derive function from microprocessors manufactured with integrated circuits containing thousands to billions of transistors. As device size decreases, so must the size of microprocessors, creating extreme manufacturing and design challenges. Modern integrated circuits are manufactured in three dimensions by depositing alternating conducting and insulating layers in a 3D arrangement to achieve maximum function in minimum size. Complex masking, depositing, and etching steps are needed to generate these 3D patterns. As sizes become smaller, mask misalignment and pinhole defects lead to significant performance losses. Area selective atomic layer deposition (AS-ALD) is a promising alternative for device construction, in which molecules are employed to mask substrates and / or surfaces. Molecular arrangement is achieved through the principles of self-assembly and preferential binding (i.e., the use of molecules that bind selectively to metals or to insulators). This technique allows patterning over large areas. It can theoretically produce patterns with molecular-level precision if sufficiently selective binding is achieved and the patterns are stable during the manufacturing process (Franzen, S., Chemical Physics Letters 2003, 387, 315, and Vericat, C., etal. Physical Chemistry Chemical Physics 2005, 7, 3258). Ligands that bind to metals and survive harsh manufacturing conditions are challenging to find.

[0011] SUMMARY

[0012] In one aspect the invention provides a compound having a structure as shown:

[0013]

[0014]

[0015] 3-benzyl-1-undecyl-4-nonyl-1 / - / - 1,2,3-triazolidene,

[0016]

[0017] 1-(2,6-diisopropylphenyl)-3-nonyl- 4-phenyl-1 H-1,2,3-triazolidene, or a hydrated or solvated form thereof, where X is an anion (e.g, hydroxide, alkoxide, halide, HCO3⁻, or triflate). In one embodiment, X is HCO3⁻.

[0018] In one aspect the invention provides a method of selective deposition, including disposing a substrate, which has a metal surface, or which includes both metal and non-metal or metal oxide, in a deposition chamber, which has a valve-controlled inlet for a carrier gas and a furnace, wherein the carrier gas has valve-controlled access to a bubbler that houses a 1,2,3-triazolium salt of Formula 1, a carboxylate zwitterion form of 1,2,3-triazole, or hydrated or solvated forms thereof, heating and maintaining the bubbler at a sufficiently high temperature to generate gaseous free 1,2,3-triazol-5-ylidene of Formula 2, that moves into the deposition chamber and selectively chemisorbs onto the metal surface, wherein substantially no 1,2,3-triazol-5-ylidene chemisorbs onto the non-metal or metal oxide surface

[0019]

[0020] (1) (2)

[0021] where X is an anion (e.g, hydroxide, alkoxide, halide, HCO3⁻, or triflate), R3is a substituted or unsubstituted C1-C12 aliphatic moiety, R1and R2are independently a substituted or unsubstituted Ci to C12 alkyl, alkenyl, or alkynyl group that is linear, branched, or cyclic, a substituted or unsubstituted aromatic moiety, or a combination thereof, wherein a substituent includes an alkyl, alkenyl, alkynyl, halo, heteroatom, and optionally two of R1, R2, and R3are joined in a cyclic structure, wherein at least one of R1and R2is an aryl moiety, an aliphatic cyclic moiety, or a heterocyclic moiety.

[0022] In one aspect the invention provides a method of deposition, including disposing a substrate in a deposition chamber, wherein the substrate has at least a metal surface, and wherein the deposition chamber includes a valve-controlled inlet for a carrier gas, and wherein the carrier gas has valve-controlled access to a bubbler that contains 1,2,3-triazolium salt, a carboxylate zwitterion form of 1,2,3-triazole, or hydrated or solvated forms thereof, heating and maintaining the bubbler at a sufficiently high temperature to generate gaseous free 1,2,3-triazol-5-ylidene or a hydrated or solvated form thereof, that moves into the deposition chamber where 1,2,3-triazol-5-ylidene, or a hydrated or solvated form thereof, chemisorbs onto the metal surface.

[0023] In one embodiment, the method further includes intermittently pulsing carrier gas that includes gaseous 1,2,3-triazol-5-ylidene into the deposition chamber and purging the deposition chamber with carrier gas.

[0024] In one aspect the invention provides a method of solution-phase selective deposition, including immersing a substrate, which has a metal surface, and a non-metal or metal oxide surface, in a container, which includes a solution that includes 1,2,3-triazolium salt of Formula 1, or a carboxylate zwitterion form of 1,2,3-triazole, and subsequently allowing 1,2,3-triazol-5-ylidene of Formula 2 to deposit on the metal surface, wherein the 1,2,3-triazol-5-ylidene selectively chemisorbs onto the metal surface, and substantially no 1,2,3-triazol-5-ylidene chemisorbs onto the non-metal or metal oxide surface, where X is an anion (e.g., hydroxide, alkoxide, halide, HCO3⁻, or triflate), where R3 is a substituted or unsubstituted Ci-012 aliphatic moiety, R1and R2are independently a substituted or unsubstituted Ci to C12 alkyl, alkenyl, or alkynyl group that is linear, branched, or cyclic, a substituted or unsubstituted aromatic moiety, or a combination thereof, wherein a substituent includes an alkyl, alkenyl, alkynyl, halo, heteroatom, and optionally two of R1, R2, and R3are joined in a cyclic structure, wherein at least one of R1and R2is an aryl moiety, an aliphatic cyclic moiety, or a heterocyclic moiety. In one embodiment, the substrate is a patterned substrate having a metal surface adjacent to a dielectric surface. In one embodiment, R3is methyl. In one embodiment, R2is phenyl. In one embodiment, the pulsing is opening the gas inlet valve for a selected time for a selected number of cycles. In one embodiment, the number of cycles is about 100. In one embodiment, the metal surface is thick enough to exhibit bulk properties. In one embodiment, the metal surface is between 0.5 to 1 000 nm thick. In one embodiment, the metal surface is between 25 and 150 nm thick. In one embodiment, the metal surface is about 100 nm thick. In one embodiment, the selected deposition temperature is in a range of about room temperature to about 500 °C. In one embodiment, the selected deposition temperature is in a range of about 30 to about 200°C. In one embodiment, the deposition chamber is suitable for holding wafers. In one embodiment, the deposition chamber is suitable for sustaining a vacuum in a range of about 0.1 torr to about 5 torr. In one embodiment, the deposition chamber is suitable for sustaining a vacuum of about 3 torr. In one embodiment, the carrier gas is nitrogen or argon. In one embodiment, purging the deposition chamber with carrier gas is performed for about 20 seconds. In one embodiment, the 1,2,3-triazol-5-ylidene chemisorbs onto the metal surface as a monolayer. In one embodiment, the 1,2,3-triazol-5-ylidene chemisorbs onto the metal surface as a bilayer. In one embodiment, the 1,2,3-triazol-5-ylidene chemisorbs onto the metal surface as a multilayer. In one embodiment, the method further includes cooling the deposition chamber to room temperature while continuously purging the deposition chamber with carrier gas. In one embodiment, the non-metal or metal oxide surface is a dielectric surface. In one embodiment, the non-metal or metal oxide surface is ZnO, SiC>2, Sisl^, HfC>2, WO3, AI2O3, or SiwOzNy wherein w is 0 to 3, z is 0 to 2 and y is 0 to 4, HfO2, or any combination thereof. In one embodiment, the method further includes removal of the 1,2,3-triazol-5-ylidene by thermal desorption to regenerate a pristine metal surface. In one embodiment, the 1,2,3-triazol-5-ylidene is a 1,2,3-triazol-5-ylidene compound shown in column 2 of Table 1, or a hydrated or solvated form thereof.

[0025] In one embodiment, the metal surface of the substrate includes Au, Cu, Ag, Ru, W, Ni, Fe, Mo, Co, Pt, Pd, or an alloy. In one embodiment, the method further includes a step of treating the substrate to refine the interface between the metal surfaces, and the non-metal or metal oxide surfaces. In one embodiment, the treating the substrate includes thermal annealing or plasma treatment. In one embodiment, the 1,2,3-triazolium salt is a precursor as shown in column 1 of Table 1 herein, or hydrated or solvated forms thereof. In one embodiment, the method further includes cleaning the substrate prior to the deposition of 1,2,3-triazol-5-ylidene. In one embodiment, the cleaning the metal surface includes exposing it to hot plasma. In one embodiment, the hot plasma is a plasma of H2at about 400°C. In one embodiment, the method further includes modifying the temperature of the deposition chamber to a selected deposition temperature if the deposition temperature differs from a temperature of cleaning. In one embodiment, the method further includes evacuating the deposition chamber such that it is under vacuum prior to the deposition of 1,2,3-triazol-5-ylidene. In one embodiment, the method further includes annealing the substrate after 1,2,3-triazol-5-ylidene deposition.

[0026] An aspect of the invention provides use of a salt of Formula 1 or a carboxylate zwitterion form thereof, for generation of gaseous free 1,2,3-triazol-5-ylidene of Formula 2 for deposition onto a metal surface

[0027]

[0028] (1) (2) where X is an anion (e.g., hydroxide, alkoxide, halide, HCO3⁻, or triflate), R3is a substituted or unsubstituted C1-C12 aliphatic moiety, R1and R2are independently a substituted or unsubstituted Ci to C12 alkyl, alkenyl, or alkynyl group that is linear, branched, or cyclic, a substituted or unsubstituted aromatic moiety, or a combination thereof, wherein a substituent is an alkyl, alkenyl, alkynyl, halo, heteroatom, and optionally two of R1, R2, and R3are joined in a cyclic structure, wherein at least one of R1and R2is an aryl moiety. In one embodiment, R3is methyl. In one embodiment, R2is phenyl.

[0029] BRIEF DESCRIPTION OF THE DRAWINGS

[0030] For a better understanding of the invention and to show more clearly how it may be carried into effect, reference will now be made, by way of example, to the accompanying drawings, wherein:

[0031] Fig. lAshows synthesis of triazolium hydrogen carbonate salts. Fig. 1B shows optimized conditions for solution phase and vapor phase deposition on gold on silicon wafers.

[0032] Fig. 1C shows representative N 1s XPS regions forTz SAMs prepared by solution deposition.

[0033] Fig. 1D shows a table summarizing N 1s of XPS data, estimated film density (p), water contact angle (0W), work function (<t>) and thermal desorption temperature (Tmax)for NHC and Tz SAMs on gold, where TzlPr,lPrdescribes R1= R2= iPr.

[0034] Fig. 2A shows thermograms for TzR1«H2CO3, which indicate thermal events including loss of water to form a carboxylate zwitterionic derivative, dissociation of CO2to form free carbene, and volatilization of the free carbene.

[0035] Fig. 2B shows proposed thermal activation pathway including heating a 1,2,3-triazolium bicarb salt to generate a carboxylate zwitterionic form, and applying heat to form free Tz; sample loading (5 ± 0.1 mg) and heating rate (10 °C min-1).

[0036] Fig. 2C shows a table summarizing thermal properties for triazolium hydrogen carbonate salts; TH2O = volatilization temperature for water, Tco2 = volatilization temperature for CO2, TD= thermal decomposition temperature, and N. D = not determined.

[0037] Fig. 3A shows a scheme for dielectric depositions with ZnEt2and H2O.

[0038] Fig. 3B shows a ToF-SIMS image for an area selective deposition of TzDippon Au, where the species that appears in yellow is Tz free carbene M+ion.

[0039] Fig. 3C shows a ToF-SIMS image for ZnO growth on a TzDipp-protected Au / SiC>2 patterned wafer, where the species that appears in yellow is ZnO" ion.

[0040] Fig. 3D shows an SEM (scanning electron microscopy) image of ZnO growth on SiO2 only.

[0041] Fig. 3E shows QCM (Quartz Crystal Microbalance) traces of ZnO depositions on AI2O3, Au, and TzDippfunctionalized Au QCM crystals.

[0042] Figs. 4A-C show ToF-SIMS imaging of Tz depositions on substrates that were patterned with Au bands and SiO2 bands, where species that appear in yellow are specified under each image. Fig. 4C shows ToF-SIMS imaging for TzlPr,lPrprotected Au / Si02 patterned wafers after ZnO deposition, where the colour grading represents the intensity of the M+ ion signal indicated.

[0043] Fig. 4D shows TOF-SIMS ion intensity mapping for Cu, Co, and Ru pattern, where S is a calculated selectivity value.

[0044] Fig. 4E shows SEM and EDS element mapping for Cu, Co, and Ru pattern sample. Si, Hf, mapping element represented forSiO2, HfO2, respectively. Scale bar was 100 urn.

[0045] Fig. 4F shows SEM and EDS element mapping for HfO2 AS-ALD in the large region of multiple Au / SiO2 bands, wherein Si, Hf, and C element represented SiO2, HfO2, and Tz Dipp, respectively, and scale bar was 100 urn.

[0046] Fig. 5A-H shows plots of low energy XP spectra of specified Tz that have been vapor deposited on gold supported silicon wafers; tangent lines have been drawn to depict an x-intercept from which work function energies were obtained; note that comparison NHC iP^bimy was solution deposited.

[0047] Fig. 6 shows a control high-resolution XPS spectra of Au wafer after MeOH treatment.

[0048] Fig. 7 shows a high-resolution XPS spectra of TzDippon Au, for Au, C, N, and O, as indicated.

[0049] Fig. 8 shows a high resolution XPS of C 1s and N 1s forTzDippdeposited on Au metal by atomic layer deposition.

[0050] Fig. 9 shows ToF- SIMS ion mapping images for Au pattern after Tz deposition, where S is a calculated selectivity value.

[0051] Fig. 10A SEM spectrum mapping for HfO2 AS-ALD in a small region of Au / SiO2, wherein scale bar was 1 urn

[0052] Fig. 10B shows and EDS spectrum mapping for HfO2 AS-ALD in a small region of Au / SiO2, wherein scale bar was 1 urn

[0053] DETAILED DESCRIPTION OF EMBODIMENTS

[0054] As used herein, a “metal” is any of a class of substances characterized by high electrical and thermal conductivity as well as by malleability, ductility, and high reflectivity of light.

[0055] As used herein, the terms “physisorb” “physisorption” or “physical adsorption” mean adsorption in which the forces involved are intermolecular forces (e.g., van der Waals forces).

[0056] As used herein, the terms “chemisorb” or “chemical adsorption” mean adsorption in which the forces involved are valence forces of the same kind as those operating in the formation of chemical compounds.

[0057] As used herein, the term “dielectric material” means a substance that is a poor conductor of electricity, but an efficient supporter of electrostatic fields (i.e., insulator).

[0058] As used herein, the term "self assembled monolayer" can represent a dense packed monolayer or a less organized, less dense overlayer of an organic material.

[0059] An organic ligand called triazolylidene (Tz), which is structurally related to N-heterocyclic carbenes, has been investigated in Area-Selective Atomic Layer Deposition (AS-ALD) processes described herein. Tz has been shown to form strong bonds to many metal surfaces. These robust molecules protect metal surfaces and provide a solution to the challenges of electronic device manufacturing.

[0060] A metal surface refers to a metallic portion of a substrate, that is accessible to vapor deposition. The metallic portion may be the accessible layer of a bulk metal, or it may be a metallic coating that is located on a support. The support can be made of another substance such as a different metal than the metal of the metallic coating, or a non-metal such as zinc oxide (ZnO), silicon, indium tin oxide (ITO), alumina (AI2O3), glass, etc.

[0061] Tz can be used as removable small molecule masks (i.e., films, coatings) and inhibitors to prevent deposition of other materials. As described herein, Tz have been shown to bind selectively to metal surfaces in the presence of non-metal or metal oxide materials. Examples of metals include, but are not limited to Au, Cu, Ag, Ru, W, Ni, Fe, Mo, Co, Pt and Pd, and alloys such as bronze and steel. Examples of non-metal surfaces or metal oxide surfaces include ZnO, SiO2, Si3N4, AI2O3, SiwOzNywherein w is 0 to 3, z is 0 to 2 and y is 0 to 4, HfO2, or any combination thereof.

[0062] Among methods for device fabrication, organic molecules that chemisorb selectively to metal surfaces have led to the development of this method of small molecule inhibitors for selective area deposition. In this approach, the small molecule coating acts as protecting groups such that the metal is protected from reaction with unwanted entities. Examples of reactive entities that have been used to test the durability of the Tz coating, are trimethylaluminum (TMA), triethylaluminium (TEA) and diethylzinc (DEZ), which were used to deposit dielectric layers on metal after exposure to water as a co-reactant. In the absence of a protective surface film, these species and water react with metal to form a metal oxide coating. In selective area deposition, an organic surface species (i.e., surfactant) acts as an inhibition layer during dielectric deposition and growth. This technique is functionally simple, allows patterning over large areas, and can maintain the picometer scale resolution that atomic layer deposition (ALD) is known for.

[0063] As described herein, a series of 1,2,3-triazolylidenes (Tz) were deposited on gold (Au) and Au / SiO2patterned substrates. Triazolylidenes are an important class of stable carbenes that can be prepared using click chemistry, followed by an SN2 reaction and then anion exchange. Anions can include any charge- balancing anion that enables or supports conversion into a triazolylidene. Selective deposition was studied using precursor salts which were 1,2,3-triazolium bicarbonate salts or 1,2,3-triazolium triflate salts. Thermal properties of the precursors were measured and shown to be appropriate for either solution phase or vapor phase deposition. Tz self-assembled monolayer (SAM) stability was studied by time-of-flight secondary-ion mass spectrometry (ToF-SIMS) of Tz SAMs before and after exposure to various conditions, leading to the conclusion that Tz-SAMs have good thermal stability. Tz-SAMs were analyzed using X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) and contact angle measurements. High selectivity for deposition on metal regions over dielectric regions was observed on patterned Au / SiO2substrates. Tz’s were shown to be a class of small molecule inhibitors that prevent ZnO deposition (see Figs. 3C, 3D, and 3E). These properties provide utility in microelectronics fabrication methods.

[0064] As described herein, Tz-SAMs are useful as small molecule inhibitors (SMIs) to temporarily mask metal surfaces during growth of non-metallic regions. This process is used in bottom-up fabrication within the semiconductor industry.

[0065] As described in the Examples and Figures, synthesis of Tz bicarbonate salt precursors was achieved and their conversion into SAMs on metal (e.g., Au) was studied. These SAMs exhibited good thermal stability. Referring to Fig. 2A to 2C, thermograms are shown for TzR1«H2CO3, which indicate thermal events including loss of water to form carboxylate zwitterionic derivative, dissociation of CO2to form free triazolylidene, and volatilization of the free triazolylidene. Tz-based SAMs also demonstrated high preference for metal surfaces when in the presence of metal surfaces and dielectric surfaces (see Fig.

[0066] 3B and Figs. 4A-4C). Inhibition of dielectric deposition onto Tz-protected metals was also studied (see Fig. 3D and 3E).

[0067] Several different characterization techniques are reported on herein. These include Energy Dispersive Spectroscopy (EDS) and Scanning Electron Microscopy (SEM).

[0068] EDS is typically used to determine the elemental composition of a sample surface. By measuring elemental composition of different regions on a patterned wafer, EDS quantitatively confirms the selective inhibition of dielectric materials as the dielectric elemental signals (ex. Zn, Hf, etc.) should not be present on a protected regions. As example of a protected surface is one on which a triazolylidene is effectively bound. EDS data provides the percentage of the sample surface that has an element of interest. For example, on a region of a sample surface, EDS provides percentages of C, N, O, Au, and Zn. If an area is effectively protected against growth of ZnO, it is expected that there will be zero %Zn on that area. In contrast, an area that is not effectively protected, will show a nonzero %Zn. In studies herein, Tz-protected regions would have zero %Zn, whereas for a SiC>2 (dielectric) region, which is not protected by Tz, it is expected that there will be a non-zero %Zn value. The difference in %Zn between two regions determines the effectiveness of the inhibition. The thickness of the ZnO films is determined by SEM. EDS only penetrates to a certain depth. It is expected that a greater %Zn will be found for areas that do not inhibit ZnO growth. For example, triazole regions may have <10% Zn whereas the dielectric regions will have >10% Zn. In this way, it is possible to learn how much material is deposited on which areas of a patterned wafer.

[0069] SEM may be used to visually observe the presence of dielectric materials on a surface of a metal wafer. Dielectric metals deposited (e.g., ZnO) typically are present as macroscopic ZnO crystals, which can be observed under a scanning electron microscope. Selective inhibition was demonstrated visually and qualitatively using the SEM technique on Au / SiO2 patterned substrates wherein the Au portions were protected by TzDipp, Tzd"Pr, or TzlPrin the presence of ZnO deposition conditions.

[0070] SEM was also used to confirm ZnO film thickness. ZnO thicknesses was assessed for TzDipp-protected Au regions on Au / SiO2 patterned wafers using SEM. Microscopy was performed using a LEO 1540XB SEM with an accelerating voltage of 5 kV. Cross-sections were formed by depositing -100 nm of Pt and etched using a Zeiss 1540XB focused ion beam. The thickness of the ZnO growth on Au / SiO2 patterned substrates were measured to be around 190 nm on the SiO2 bands and 0 nm growth on Tz protected Au regions.

[0071] A method of deposition was exemplified that included placing a substrate, which had at least a metal surface, in a deposition chamber. The deposition chamber included a valve-controlled inlet for carrier gas. The carrier gas had valve-controlled access to a bubbler that contained a salt of Tz (e.g., Tz’HCOs or Tz«triflate), which was used as a precursor of free Tz. The salt of Tz has a counterion that is any charge-balancing anion that enables or supports conversion into a triazolylidene. In one embodiment, the counter ion can also act as a base. Such salts form a stable precursor form of the Tz. In the examples herein, a description is provided of thermolysis of shelf-stable Tz bicarbonate salts to generate a carboxylate adduct through a dehydration reaction, and then generation of a free Tz through a decarboxylation reaction (see Figs. 2A and 2B). In some embodiments, the substrate was cleaned (e.g., by hot plasma) before deposition of the small molecule layer. If necessary, the temperature of the deposition chamber can be modified from a cleaning temperature to a selected deposition temperature. The bubbler containing the Tz precursor was then heated and maintained at a sufficiently high temperature to generate gaseous free carbene that collected in a headspace of the bubbler. At this point, intermittently and repeatedly, carrier gas, which included gaseous Tz, was pulsed into the deposition chamber (e.g., for about 5 seconds). After each pulse, the deposition chamber was purged with carrier gas (e.g., for about 60 seconds). Once approximately 5 to 30 pulses had been performed, the deposition chamber was allowed to cool to room temperature while being continuously purged with carrier gas. Purging the deposition chamber with carrier gas was performed to substantially remove physisorbed species. Using this method, Tz chemisorbed onto the metal surface in a self-saturating manner.

[0072] In a selective deposition process, a method of deposition is provided that includes disposing a patterned substrate in a deposition chamber, the patterned substrate has a metal surface, and a non-metal or metal oxide surface. The deposition chamber included a valve-controlled inlet for carrier gas. The carrier gas had valve-controlled access to a bubbler that contained a Tz precursor (e.g., salt of Tz). In some embodiments, the substrate had been cleaned (e.g., by hot plasma) prior to exposure to Tz vapors. If necessary, the temperature of the deposition chamber can be modified from a cleaning temperature to a selected deposition temperature. The bubbler containing the Tz precursor was then heated and maintained at a sufficiently high temperature to generate gaseous free carbene that collected in a headspace of the bubbler. At this point, intermittently and repeatedly, carrier gas, which included gaseous Tz, was pulsed into the deposition chamber (e.g., for about 60 seconds). After each pulse, the deposition chamber was purged with carrier gas (e.g., for about 20 seconds). Once approximately 100 pulses had been performed, the deposition chamber was allowed to cool to room temperature while being continuously purged with carrier gas. Purging the deposition chamber with carrier gas was performed to remove physisorbed species. Using this method, Tz chemisorbed onto the metal surface in a selfsaturating manner and substantially no Tz chemisorbed onto the non-metal or metal oxide surface.

[0073] Designing metallic patterns on integrated circuits could change the way semiconductors are manufactured. Such patterns would enable smaller features and better performance.

[0074] Traditional device fabrication techniques involve top-down strategies composed of multiple cycles of etching and lithographic steps. As device miniaturization progresses, the errors associated with top-down fabrication methods become problematic and new strategies are needed. Area-selective atomic layer deposition (AS-ALD) is a promising fabrication technique which relies on differences in local surface environment.

[0075] In one embodiment, a further step was performed of treating the substrate to refine the interface between the metal surfaces, and the non-metal or metal oxide surfaces.

[0076] Examples of such treating include thermal annealing, and plasma treatment. See Figs. 4A-4C for more information about the effect of thermal annealing and refinement of the interfaces.

[0077] Tz-SAMs can be cleanly removed after use by thermal desorption to afford pristine metallic surfaces. Therefore, Tz-SAMs are ideal candidates for passivating patterned substrates in AS-ALD.

[0078] As described herein, exemplary Tz-SAMs ((see Table 1 for structural formulae) were deposited on Au in an ALD Tool (see the Working Examples). Quality of the resultant film was assessed by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary-ion mass spectrometry (ToF-SIMS) experiments. Further studies on patterned substrates found that it was possible to deposit Tz on metal surfaces selectively, in the presence of non-metal, metal oxide, or dielectric surfaces. Referring to Fig. 4A-4C, several Tz were successfully selectively deposited on the metal areas of patterned substrates bearing side-by-side areas of exemplary metals (e.g, Au), and exemplary dielectric (e.g., SiO2) surfaces.

[0079] Parameters, such as the pulse time for introducing the Tz and the “soak” time to help ensure full coverage were optimized. However, these experiments, while useful in determining essential parameters in tandem with XPS, were often qualitative in their determination of full surface coverage. Analysis by ToF-SIMS was used to optimize the deposition parameters.

[0080] To understand selective deposition of Tzon patterned metal surfaces, ToF-SIMS imaging was employed. ToF-SIMS provides mass spectrometry. Masses can be correlated to species within the system. After functionalizing patterned substrates with Tz, surfaces were imaged by probing for different possible ions that could be observed. These images show ejected Si+from areas that were expected to be composed of SiO2, and M+ ions in samples in metal areas. Referring to Figs. 3B, 3C, 4A-4D, and 9, ToF-SIMS images are shown for specified Tz on a mixed SiO2 / Au sample, prepared with alternating metal and silicon oxide layers. The ToF-SIMS data confirmed that substrate patterning was obtained and that the Tz preferentially chemisorbed to the metal surfaces in the presence of the silicon oxide dielectric layer, and substantially no Tz were present on the dielectric surface of each sample.

[0081] The following working examples further illustrate the invention and are not intended to be limiting in any respect. Working Examples

[0082] Starting materials were purchased from Sigma Aldrich or Fischer Scientific unless otherwise specified.

[0083] All synthetic reactions were conducted under air unless otherwise stated. Solvents were used without purification except where stated. Unless otherwise noted, chemicals were purchased from chemical suppliers at highest purity and used as received. N2was 99.999% pure unless stated otherwise and was available from Praxair. Amberlyst A26 hydroxide resin was activated by sparging a solution with CO2for 30 minutes before use as the HCO3 resin.

[0084] 1H and13C{1H} Nuclear Magnetic Resonance (NMR) spectra were recorded at University of Western or Queen’s University on Bruker Avance-400 or 600 MHz spectrometers at 298 K. Chemical shifts (5) are reported in parts per million (ppm) and are internally referenced to residual protonated (1H) or deuterated (13C{1H}) solvent signals, which are themselves set relative to Si(CH3)4. Chemical shifts of known solvent impurities were referenced to the literature. Coupling constants (J) are reported in Hz as absolute values. All NMR data were processed and displayed using Bruker TopSpin or MestReNova software programs.

[0085] Elemental analyses were performed at Queen’s University using Flash 2000 CHNS-0 analyzer. Electrospray ionization mass spectra (ESI-MS) of small molecules were recorded using a Thermo Fisher Orbitrap VelosPro mass spectrometer with a heated-electrospray ionization probe.

[0086] XPS spectra were recorded on a Kratos Nova AXIS spectrometer equipped with AIN X-ray source. Samples were mounted on an aluminum sample holder using double-sided adhesive copper tape and kept under high vacuum (10“8Torr) overnight inside the preparation chamber before being transferred to the analysis chamber (ultra-high vacuum, 10’10Torr).

[0087] Data were collected using Al Ka radiation operating at 1486.69 eV (150 W, 15 kV), charge neutralizer and a delay-line detector (DLD) consisting of three multichannel plates. Acquired data were processed using CasaXPS software following reference handbooks. Processed data were plotted in Python using Matplotlib package. Elemental compositions of samples were evaluated by running widescan at 160 eV pass energy. After peak identification, high resolution scans were performed for O 1s, C 1s, N 1s, and substrate of interest regions. These scans were performed at 20 eV pass energy. C 1s spectra were peak fitted following guidelines from reference handbooks and C-C / C-H peak was charge corrected to 284.8 eV. Unless otherwise mentioned, a Shirley type background correction was used for all spectra shown here.

[0088] Deposition and characterization studies of the resultant films (e.g., XPS, ToF-SIMS) were conducted. Depositions were carried out in a standard Picosun R200 thermal ALD tool. Depositions were standard pulse-purge cycles (e.g, 100 cycles; 10 s pulse NHC, 10 s N2 purge, with various substrates. Durability studies of monolayer deposition films were conducted a custom thermal ALD tool.

[0089] Nuclear Magnetic Resonance (NMR)

[0090] 1H,13C and19F NMR spectra were recorded using Bruker Avance-400, 600 or 700 MHz spectrometers at 298 K. Chemical shifts (5) are reported in parts per million (ppm) and referenced relative to an internal standard 5 3.31 (CD3OD) for1H, 8 49.00 (CD3OD) and19F NMR spectra are referenced to an external standard 8F= 0 ppm (CFCI3). Coupling constants (J) are reported as absolute values with splitting patterns denoted as s (singlet), d (doublet), t (triplet), q (quartet), sept (septet), m (multiplet), and br (broad). All NMR data were processed and displayed using Bruker TopSpin software or MestreNova.

[0091] Elemental Analysis (EA) and Infrared Spectroscopy (IR)

[0092] Elemental analyses were performed using a Flash 2000 CHNS-0 analyzer. Infrared spectroscopy was performed using an Agilent Cary 630 FT-IR benchtop spectrometer.

[0093] Electron Spray Ionization Mass Spectrometry (ESI-MS)

[0094] Mass spectrometry analyses was performed using Thermo Scientific Orbitrap Velos Pro Mass Spectrometer.

[0095] X-ray Photoelectron Spectroscopy (XPS)

[0096] X-ray photoelectron spectra were recorded on a Kratos Nova AXIS spectrometer equipped with AIN X-ray source. Samples were mounted on an aluminum sample holder using double-sided adhesive copper tape and kept under high vacuum (10‘8Torr) overnight inside the preparation chamber before being transferred to the analysis chamber (ultra-high vacuum, 10‘1° Torr). Data were collected using Al Ka radiation operating at 1486.69 eV (150 W, 15 kV), charge neutralizer and a delay-line detector (DLD) consisting of three multichannel plates. Elemental compositions of samples were evaluated by running survey scans at 160 eV pass energy. Both the survey scan and high-resolution scans were collected at a take-off angle of with an analysis area of 300 x 700 microns. After peak identification, high-resolution scans were performed at 20 eV pass energy for F 1s, O 1s, N 1s, C 1 s, Au 4f regions. CasaXPS software was used for all deconvolution of spectra following reference handbooks. All spectra were calibrated to a binding energy (BE) of 284.8 eV for C (1s) C-C / C-H peaks. Shirley (C, O, metal) or linear (N) background subtractions were used unless otherwise indicated. Mixed Gaussian-Lorentzian lineshapes were used for peak fitting; Au, Ag and Cu were fit using GL(90) while all other elements were fit using GL(30). Surface coverages were estimated using the formula described elsewhere (see Kim, H. K., etal. Chem. Mater. 2017, 29, 3403-3411.)

[0097] ■ 1.19 x 1016cm-2

[0098]

[0099] A VAu /

[0100] Equation 1. Surface coverage formula.

[0101] Where A / N is the number of nitrogen atoms, A is area, and / N and / Auare the corrected N 1s and Au 4f signal intensities, respectively.

[0102] Low Energy XPS

[0103] Low energy x-ray photoelectron spectroscopy measurements for work function calculations were obtained at the National Synchrotron Radiation Research Center (NSRRC) using beamline TLS 09A2. The data were collected using a Scienta Omicron R3000 Electron Spectrometer. The beamline was calibrated to the binding energy of Au (84.0 eV) prior to all measurements. Data were measured using an incident energy of 130 eV and a pass energy of 20 eV was used. A negative 5 eV bias was applied, and the resulting data was calibrated manually to account for this bias. The work function was obtained by drawing a line tangent to the x-axis and the secondary electron cutoff, followed by extrapolating the intercept between the two lines.

[0104] Contact Angle

[0105] Contact angle measurements were obtained using an OCA 25 contact angle analysis instrument with the SA 20 contact angle analysis software. A 5 pL drop of milliQ water was used for all measurements. Contact angles were measured on Tz solution deposited gold on silicon wafers that were dried under vacuum in a dessicator at least 24 h prior to measurement.

[0106] ToF-SIMS

[0107] Samples were examined using an ION-TOF (GmbH) TOF-SIMS IV equipped with a Bi cluster liquid metal ion source. A pulsed 25 keV Bi3+cluster primary ion beam was used to bombard the sample surface to generate secondary ions with a current of 1pA. The positive (or negative) secondary ions were extracted from the sample surface, mass separated and detected via a reflectron-type of time-of-flight analyser. Reflector values for the positive and negative mode were +16V and -36V, respectively. Sample charging was neutralised with a pulsed, low energy electron flood. Ion mass spectra were collected in an area of 500 pm x 500 pm at 128x128 pixels with 20 scans. High-resolution imaging spectra were collected with of 500 pm x 500 pm at 128x128 pixels with 100 scans, processed on the ION-TOF software and normalized to the total yield by a division normalization factor. Mass spectra were processed on ION-TOF software with a binning value of 256 and calibrated to H+, C+, and C2H5+mass signals.

[0108] ToF-SIMS selectivity measurements

[0109] The assessment of Tz selectivity through ToF-SIMS imaging involved the categorization of metal bands as growth areas and dielectrics as non-growth areas. Within the ION-TOF software, a region of interest (ROI) was designated for either metal or dielectric areas and subsequently correlated with the respective bands on the wafer. Ion intensities, specifically Au+for metal bands and Si+for dielectric bands, were extracted from ToF-SIMS mass spectra, with the metal and dielectric ROIs applied. To determine the selectivity values for the Tz, the ROI of the metal bands (0Growth Area) and the ROI of the dielectrics (0Non-Growth Area) were applied to the patterned wafer. The ion intensity of the Tz was measured, and the signal was then normalized against the total ion yield, which encompasses Au, dielectric (Si+), and Tz ions. The resulting selectivity value (S) should fall within the range of 1 > S -1, 1 being perfect selectivity for the growth area and -1 being perfect selectivity for the non-growth area. These values, representing both the ion yield fraction on the growth area and the non-growth area, were utilized in equation 2.

[0110] n _ nn!.... °Growth Area °Non-Growth Area

[0111] Selectivity = — - - -

[0112]

[0113] ^Growth Area + ^Non-Growth Area

[0114] Equation 2. Selectivity formula for the deposition of Tz on patterned substrates.

[0115] Thermal Desorption Studies

[0116] All vacuum annealing studies were carried out on a VWR Symphony Vacuum Oven equipped with an Edwards RV12 Rotary Vane Vacuum Pump. Tz coated Au substrates were placed on a glass dish and introduced into the pre-heated vacuum oven at 150 to 200 °C for 1 hour. The heating and cooling cycles were set to 0.5°C / min with a working pressure of 15 Torr. After vacuum annealing, samples were removed from the oven and placed in storage under atmospheric conditions until analysis was conducted. ToF-SIMS samples were collected before and after thermal treatment and normalized to Au (Aus+). Five spots on the Au wafers were collected and averaged for both the M+and Au3+signals. Spectra intensities were calculated to be a percentage of the initial deposition M+intensity of the Tz monolayer.

[0117] (SEM) Scanning Electron Microscopy

[0118] Microscopy was performed using a LEO 1540XB SEM with an accelerating voltage of 5 kV. Cross-sections were formed using a Zeiss 1540XB focused ion beam.

[0119] Energy Dispersive Spectroscopy (EDS) All energy dispersive spectroscopy (EDS) measurements were conducted on an Oxford Instruments system using an accelerating voltage of 5 kV.

[0120] Example 1. Synthetic Procedures and Characterization of Compounds

[0121] A series of triazolium hydrogen carbonate salts TzR1«H2CO3 were prepared, with varying R1and R2substituents (see Fig. 1A and Table 1). Click reactions were employed to introduce R2through an alkyne moiety and R1through alkylation. Ns-methylation followed by treatment with an HCO3- ion exchange resin gave the desired Tz precursors.

[0122] After ion exchange, new signals for the HCO3⁻ anion appeared in the13C{1H} NMR spectra (de = 161.4) and strong vibrations for C=O and C-0 functional groups were observed in the IR spectra (v= 1631, 1604, 1393 cm'1). Characterization of the Tz salts included1H NMR,13C{H} NMR, infrared spectroscopy and elemental analysis.

[0123] Example 1A. Synthesis of Triflate Precursor [HOTf][TzDipp]

[0124] Starting triazole and triazolium triflate salt precursors for TzDippwere prepared following a literature procedure (see Guisado-Barrios, G. et al., Angew. Chemie. Int. Ed. 2010, 49, 4759-4762).

[0125] 0 OTf Me ‘BuONO / SifMesJsNs N=N MeOTf N=N®

[0126] Dipp— Dipp— CH3CN, 0°C toluene, rt

[0127] [HOTf|[TzDipp]

[0128]

[0129] Synthetic scheme for preparation of [HOTf][TzDipp

[0130] Example 1B. Synthesis of Iodide Precursors [HI][TzR1]

[0131] Starting triazoles were prepared according to literature procedures (Feldman, A. K., et al., Org. Lett. 2004, 6, 3897-3899). Triazoles (1 eq) were added to a 150 mL pressure flask with a stir bar. lodomethane (5 eq) and acetonitrile (30 mL) were added to the flask before heating to 80 °C and stirring overnight. The acetonitrile was evaporated off resulting in a yellow or red oil. Ethyl acetate was added to the oil and the iodide salt precipitated immediately. If precipitation did not occur immediately, the flask was shaken and sonicated and all precursor salts precipitated out of solution. The salts were triturated in ethyl acetate (3 x 30 mL), filtered and volatiles removed in vacuo to afford pale yellow to off white powders (75-90%). L-Proline Na2CO3NaN3CuSO4* 5 H2O1Me Na Ascorbate Me - 1 N=N® R1~ H + R2-X R2-N\^^RI 9:1 DMSO: H2O MeCN 24 h, 60 °C 24 h, 80 °C X = Cl, Br, I [HI][TZR1]

[0132]

[0133] 82 - 98 % 75 - 90 % Synthetic scheme for preparation of triazolium iodide precursors [HI] [TzR1]

[0134] Example 1C. Synthesis of triazole derivatives with long alkyl chains

[0135] General synthesis

[0136] NaN3

[0137] R^Br

[0138]

[0139] - ► R‘ N3

[0140] DMSO, rt, 24 h

[0141] Primary or secondary bromoalkane (1.0 eq) was added to a 250 mL round bottom flask containing a stir bar and DMSO was added after while stirring. Sodium azide (1.2 eq) was added afterwards to the DMSO solution before stirring the resulting mixture at room temperature for 24 h. The resulting mixture was quenched with water after 24 h and extracted with ethyl acetate. The organic layer was dried over sodium sulfate before concentrating under reduced pressure. The crude product was used without further characterization.

[0142] CuSO4• 5 H2O R2

[0143] Na Ascorbate

[0144] R1-= + R2“N3

[0145]

[0146] H2O, rt, 24 h

[0147]

[0148] Organic azide (1.0 eq) was added to a 250 mL round bottom flask containing a stir bar. Sequential addition of copper sulfate pentahydrate, sodium ascorbate, and alkyne (1.1 eq) followed before dissolving all compounds in water. The resulting water mixture was stirred for 24 h at room temperature. After the elapsed time, the reaction was quenched with an aqueous ammonium hydroxide solution before extracting with dichloromethane. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The resulting crude powder was triturated with hexanes to remove any remaining impurities.

[0149] With this synthesis, it is possible to prepare a triazole ring with any chain length on its R1and R2positions. A primary or secondary bromoalkane is chosen and an alkyne. Synthesis of 3-benzyl-1-undecyl-1-nonyl-1 / - / -1,2,3-triazolidene

[0150] The above general synthesis was used to prepare 1-benzyl-3-undecyl-4-nonyl-1 / - / -1,2,3-triazole. The organic azide was 1 -azidoundecane, and the alkyne was undec-1-yne.1H NMR (600 MHz, CD3OD): d 7.42-7.45 (m, 3H), 7.35 - 7.38 (m, 2H), 5.82 (d, J = 12.0 Hz, 2H), 4.99 (t, J = 7.2 Hz, 1 H), 4.63 (t, J = 7.1 Hz, 1 H), 3.08 - 3.11 (m, 1H), 2.83 -2.85 (m, J= 1H), 1.97 -2.05 (m, 2H), 1.60 (p, J = 7.7 Hz, 1 H), 1.28 - 1.34 (m, 18 H, 3 x CH2and isopropyl CH3overlapping), 1.19 - 1.20 (m, 2H), 0.90 (t, J= 7.1 Hz, 9 H).13C NMR (150 MHz, CD3OD): d161.45, 146.01, 137.81, 134.02, 133.57, 130.56, 130.48, 130.45, 129.37, 129.23, 55.50, 55.08, 54.23, 33.07, 30.73, 30.62, 30.59, 30.49, 30.40, 30.32, 30.21, 30.16, 30.00, 29.90, 29.10, 28.18, 27.26, 27.17, 24.68, 24.25, 23.72, 14.43.

[0151] Example 1D. Synthesis of nonyl trifluoromethanesulfonate (10)

[0152] K2CO3

[0153]

[0154] + Tf2O _ TfO CH2CI2I0 °C to rt, 6 h 10

[0155] 1 -nonanol (1.0 equiv.) was added to a 20-dram vial containing a stir bar, dissolved in dichloromethane, and left to cool in the freezer to 0 °C. Upon cooling to 0 °C, anhydrous potassium carbonate (1.1 equiv.) was added followed by dropwise addition of trifluoromethanesulfonic anhydride (1.2 equiv.). The vial was sealed, and the reaction was allowed to stir for 6 hours while warming up to room temperature naturally. After the elapsed time and the colour change of the mixture from colourless to orange, the reaction was filtered through a syringe filter to yield the crude product (10) as a solution in dichloromethane. The crude product was used without further purification. Characterization was not performed due to the high instability of this compound.

[0156] Example 1E. Synthesis of 1-(2,6-diisopropylphenyl)-3-nonyl-4-phenyl-1H-1,2,3-triazol-3-ium trifluoromethanesulfonate (20)

[0157] CH2CI2, rt, 18 h

[0158]

[0159] In a 20-dram vial equipped with a stir bar was added a solution of 1 -(2,6-diisopropylphenyl)-4-phenyl-1 / - / -1,2,3-triazole in dichloromethane, followed by the dropwise addition of 10 in dichloromethane (2.0 equiv.). Once the addition of 10 was complete, the dichloromethane was evaporated under reduced pressure and the resulting slurry was allowed to stir for 18 h at room temperature. After the elapsed time the vial was removed from the glovebox and the reaction was quenched by the addition of methanol followed by stirring for 15 minutes. Chloroform and water were added to the mixture and the aqueous layer was extracted twice with chloroform. The combined organic phases were then washed twice with brine, dried over sodium sulfate, and concentrated under reduced pressure to yield the crude product. Subsequent purification of the product was achieved through flash chromatography (ethyl acetate / hexanes), yielding 20 as an amber oil (0.105 g, 93%).1H NMR (400 MHz, CDCl₃) δ8.64 (d, J = 1.2 Hz, 1 H), 7.84 (dd, J = 6.7, 2.9 Hz, 2H), 7.67 - 7.62 (m, 3H), 7.39 (d, J = 7.9 Hz, 2H), 4.83 (t, J = 7.1 Hz, 2H), 2.34 (hept, J = 6.7 Hz, 2H), 1.95 (p, J= 7.2 Hz, 2H), 1.26 (d, J = 6.7 Hz, 14H), 1.22 - 1.16 (m, 12H), 0.89 - 0.81 (m, 3H);13C NMR (101 MHz, CDCl₃) δ 145.7, 144.4, 133.1, 132.4, 131.0, 130.1, 124.9, 121.5, 52.9, 31.8, 29.3, 29.2, 29.0, 28.9, 26.2, 24.7, 23.7, 22.7, 14.2;19F NMR (376 MHz, CDCl₃) δ -78.36.

[0160] Example 1 F. Synthesis of Bicarbonate Precursors

[0161] The corresponding triazolium salts [HOTf][TzDipp] and [HI][TzR1] (0.47 g, 1 mmol) were added separately to 4 mL of HCOs-anion resin in a 4 dram vial. The mixture was then suspended in 10 mL MeOH and stirred for one hour triflate salts and 30 mins for iodide salts at room temperature. The supernatant was then filtered through a glass pipette filled with Celite into a pre-weighed vial. The remaining resin was washed with MeOH (3 x 2 mL), then filtered and left to evaporate under a stream of air overnight. Then, 1.5 mL aliquots of acetone and diethyl ether were used to break up the remaining crude oil. Sonication was required to precipitate a colourless powder from the remaining oil. This powder was further sonicated with diethyl ether (2 x 3 mL) before filtration, rinsing and drying in vacuo to yield triazolium bicarbonate salts TzR1-H2CO3 as a colourless powder.

[0162] © © x MeHC°3 Me

[0163] / /

[0164] N=N® Resin-CO2N=N ®

[0165] R2-NS^^RI

[0166] MeOH - 30 mins, rt R1

[0167] Tz • H2CO3

[0168]

[0169] X = OTf, I

[0170] 73-83 %

[0171] Synthetic scheme for preparation of triazolium bicarbonate precursors (Crudden, C. M., et al., Nat. Commun. 2016, 7, 1-7). Characterization data for TzDipp-H2CO3

[0172] The characterization data for TzDipp-H2CO3 (see structural formula in Table 1) is as follows:1H NMR (CD3OD, 600 MHz) 5: 7.85 (dd, 2H,3JHH = 7.5 Hz,4JHH = 1.5 Hz), 7.73 (m, 4H), 7.54 (d, 2H,3JHH = 7.9 Hz), 4.51 (s, 3H), 2.43 (sept, 2H,3JHH = 6.8 Hz), 1.27 (d, 6H,3JHH = 6.8 Hz), 1.24 ppm (d, 6H,3JHH = 6.8 Hz). The triazolium CH resonance was not observed due to deuterium exchange with the solvent.13C {1H} NMR (CD3OD, 150 MHz) 5: 161.4 (HCO3), 147.0, 145.6, 134.2, 133.2, 132.7 (t,1JCD = 32 Hz, Tz CH(D)), 132.3, 130.8, 130.7, 126.0, 123.6, 39.9, 29.8, 24.6, 24.2 ppm. ESI-MS: Calc, m / z for [C21H26N3]+: 320.2121, [M]+. Found: 320.2077.

[0173] Anal. Calc, for C22H27N3O3- 2H2O: C, 63.29; H, 7.48; N, 10.06. *Found: C, 63.42; H, 7.12; N, 10.15. Melting Point: 123-125 °C. *Note: number of water molecules added based on the presence of water in NMR spectra and the best match to obtained elemental analysis data.

[0174] Characterization data for TzlPr iPr-H2CO3

[0175] The characterization data for TzlPr iPr-H2CO3 (see structural formula in Table 1) is as follows:1H NMR (CD3OD, 600 MHz) 5: 5.01 (sept, 1H,3JHH = 6.7 Hz), 4.26 (s, 3H), 3.28 (sept, 1 H,3JHH = 6.9 Hz), 1.67 (d, 6H,3JHH = 6.7 Hz), 1.40 (d, 6H,3JHH = 6.9 Hz). The triazolium CH resonance was not observed due to deuterium exchange with the solvent.13C {1H} NMR (CD3OD, 150 MHz) 5: 161.4 (HCO3 ), 126.1 (t,1JCD = 32 Hz, Tz CH(D)), 59.4, 37.9, 25.5, 22.2, 21.3 ppm. ESI-MS: Calc, m / z for [C9H18N3]+: 168.15, [M]+. Found: 168.1488. Anal. Calc, for C10H19N3O3-H2O: C, 48.57; H, 8.56; N, 16.99. *Found: C, 49.12; H, 9.33; N, 16.87. Melting Point: 94-96 °C.

[0176] *Note: number of water molecules added based on the presence of water in NMR spectra and the best match to obtained elemental analysis data.

[0177] Characterization data for TzMe-H2CO3

[0178] The characterization data for TzMe-H2CO3 (see structural formula in Table 1) is as follows:1H NMR (CD3OD, 600 MHz) 5: 7.7-7.6 (m, 5H), 4.40 (s, 3H), 4.31 (s, 3H). The triazolium CH resonance was not observed due to deuterium exchange with the solvent.13C {1H} NMR (CD3OD, 150 MHz) 5: 161.4 (HCO3), 133.0, 130.8, 130.7, 130.4, 123.8, 40.5, 39.3 ppm. ESI-MS: Calc, m / z for [C10H12N3]+: 174.10, [M]+. Found: 174.1001. Anal. Calc, for C11H13N3O3: C, 56.16; H, 5.57; N, 17.86. Found: C, 54.67; H, 5.43; N, 17.62. Melting Point: 50-53 °C.

[0179] Characterization data for TzEt-H2CO3

[0180] The characterization data for 1-ethyl-3-methyl-4-phenyl-1 / - / -1,2,3-triazolium- bicarbonate (TzEt-H2CO3) (see structural formula in Table 1) is as follows:1H NMR (CD3OD, 600 MHz) 5: 7.8-7.7 (m, 5H), 4.73 (q, 2H,3JHH = 7.4 Hz), 4.32 (s, 3H), 1.71 (t, 3H,3JHH = 7.4 Hz). The triazolium CH resonance was not observed due to deuterium exchange with the solvent.

[0181] 13C {1H} NMR (CD3OD, 150 MHz) 5: 161.4 (HCO3), 133.0, 130.8, 130.5, 129.1 (t,1JCD = 32 Hz, Tz CH(D)), 124.0, 50.6, 39.1, 14.5 ppm. ESI-MS: Calc, m / z for [C11H14N3]+: 188.12, [M]+. Found: 188.1158. Anal. Calc, for C12H15N3O3: C, 57.82; H, 6.07; N, 16.86. Found: C, 56.11; H, 6.03; N, 16.34. Melting Point: 142-144 °C.

[0182] Characterization data for TzlPr-H2CO3

[0183] The characterization data for 1-isopropyl-3-methyl-4-phenyl-1 / - / -1,2,3-triazolium-bicarbonate (TzlPr-H2CO3) (see structural formula in Table 1) is as follows:1H NMR (CD3OD, 600 MHz) 5: 7.72-7.71 (m, 2H), 7.69-7.65 (m, 2H), 5.1 (sept, 1H,3JHH = 6.6 Hz), 4.32 (s, 3H),1.75 (6H, d,3JHH = 6.6 Hz) The triazolium CH resonance was not observed due to deuterium exchange with the solvent.13C {1H} NMR (CD3OD, 150 MHz) 5: 161.4 (HCO3 ), 132.9, 130.8, 130.4, 59.7, 39.1, 22.3 ppm. ESI-MS: Calc, m / z for [C12H16N3]+: 202.13, [M]+. Found: 202.1314

[0184] Anal. Calc, for C13H17N3O3: C, 59.30; H, 6.51; N, 15.96. Found: C, 54.36; H, 6.81; N, 14.90. Melting Point: 128-130 °C.

[0185] Characterization data for 1-benzyl-3-methyl-4-phenyl-1 / - / -1,2,3-triazolium-bicarbonate (TzBn-H2CO3)

[0186] The characterization data for 1-benzyl-3-methyl-4-phenyl-1 / - / -1,2,3-triazolium-bicarbonate (TzBn-H2CO3) (see structural formula in Table 1) is as follows:1H NMR (CD3OD, 600 MHz) 5: 7.70-7.63 (m, 5H), 7.58-7.57 (m, 2H), 7.49 - 7.46 (m, 3H), 5.81 (s, 2H), 4.31 (s, 3H). The triazolium CH resonance was not observed due to deuterium exchange with the solvent.13C {1H} NMR (CD3OD, 150 MHz) 5: 161.7 (HCO3), 133.8, 133.2, 131.2, 131.0, 130.8, 130.7, 130.6, 129.7 (t,1JCD= 32 Hz, Tz CH(D)), 124.1, 58.7, 39.5 ppm. ESI-MS: Calc. m / z for [C16H16N3]+: 250.13, [M]+. Found: 250.1306. Anal. Calc, for C17H17N3O3-H2O: C, 62.00; H, 5.81; N, 12.76. *Found: C, 60.96; H, 5.72; N, 12.75. Melting Point: 124-126 °C. *Note: number of water molecules added based on the presence of water in NMR spectra and the best match to obtained elemental analysis data.

[0187] Characterization data for 3-benzyl-1-undecyl-4-nonyl-1H-1,2,3-triazol-3-ium bicarbonate Characterization data for 3-benzyl-1-undecyl-4-nonyl-1H-1,2,3-triazol-3-ium bicarbonate (see structural formula in Table 1) is as follows:1H NMR (600 MHz, CD3OD): 57.42-7.45 (m, 3H), 7.35 - 7.38 (m, 2H), 5.82 (d, J = 12.0 Hz, 2H), 4.99 (t, J = 7.2 Hz, 1 H), 4.63 (t, J = 7.1 Hz, 1 H), 3.08 - 3.11 (m, 1H), 2.83-2.85 (m, J= 1H), 1.97 -2.05 (m, 2H), 1.60 (p, J = 7.7 Hz, 1 H), 1.28 - 1.34 (m, 18 H, 3 x CH2and isopropyl CH3 overlapping), 1.19 - 1.20 (m, 2H), 0.90 (t, J= 7.1 Hz, 9 H).13C NMR (150 MHz, CD3OD): 8161.45, 146.01, 137.81, 134.02, 133.57, 130.56, 130.48, 130.45, 129.37, 129.23, 55.50, 55.08, 54.23, 33.07, 30.73, 30.62, 30.59, 30.49, 30.40, 30.32, 30.21, 30.16, 30.00, 29.90, 29.10, 28.18, 27.26, 27.17, 24.68, 24.25, 23.72, 14.43.

[0188] Characterization data for 1-(4-bromobenzyl)-3-methyl-4-phenyl-1H-1,2,3-triazol-3-ium bicarbonate

[0189] The characterization data for 1-(4-bromobenzyl)-3-methyl-4-phenyl-1H-1,2,3-triazol-3-ium bicarbonate (see structural formula in Table 1) is as follows:1H NMR (600 MHz, CD3OD): 87.64 - 7.70 (m, 8 H), 5.87 (s, 2 H), 4.31 (s, 3H).13C NMR (150 MHz, CD3OD): 8161.42, 145.13, 133.62, 133.01, 132.72, 132.32, 130.74, 130.51, 130.45, 125.01, 123.77, 57.62, 39.29.

[0190] Characterization data for 1,3,4-triisopropyl-1 / -7-1,2,3-triazol-3-ium bicarbonate

[0191] The characterization data for 1,3,4-triisopropyl-1 / -7-1,2,3-triazol-3-ium bicarbonate (see structural formula in Table 1) is as follows:1H NMR (600 MHz, CD3OD): 85.11 (hept, J = 7.8 Hz, 1 H), 5.03 (hept, J = 7.4 Hz, 1 H), 3.37 (hept, J = 6.6 Hz, 1H), 1.67 (t, J = 7.9 Hz, 12 H), 1.41 (d, J = 6.8 Hz, 6 H).13C NMR (150 MHz, CD3OD): 8161.41, 59.62, 56.18, 25.36, 22.77, 22.21, 22.07. See Fig. 4D forTOF-SIMS images of 1,3,4-triisopropyl-1H-1,2,3-triazol-3-ium bicarbonate deposited onto Au / Si patterned wafers. No annealing had been completed yet, but complete saturation with no selectivity was observed for the non-methylated backbone.

[0192] Example 1G. Synthesis of 1-(2,6-diisopropylphenyl)-3-nonyl-4-phenyl-1H-1,2,3-triazol-3-ium bicarbonate (30)

[0193]

[0194] In a round-bottomed flask was added compound 20 as a solution in 3:1 MeOH / H2O. To this was added excess Amberlyst-26 (available from Fisher Scientific, Ottawa, Canada) anion exchange beads, which were then saturated with bicarbonate anions via a stream of CO2 gas. The mixture was then stirred for 48 h under a constant stream of CO2. Once the anion exchange was complete, the resin was filtered off and the filtrate was concentrated under a stream of air. Once dry, the bicarbonate salt was purified through washings with cold acetone yielding 30 as a white powder (0.01 g, 10%). ToF-SIMS data confirmed the identity and selective deposition of compound 30 on patterned Au / SiO2 wafers. Compound 30 showed selectivity for Au.

[0195] Example 2. Thermal Characterization of Bicarbonate Precursors

[0196] TGA and DSC was performed on a Mettler Toledo TGA / DSC 3+ instrument. For TGA, 5.000 ± 0.1 mg of analyte was placed in a platinum pan and was heated until complete volatilization or the max temperature of the instrument with a ramp rate of 10 °C / min, under N2(99.999% purity, 60 seem) as the purge gas. Temperature of volatilization (Tv)(at 1 Torr) were extrapolated using the Clausius-Clapeyron relation. Platinum pans were cleaned by sequential sonication in glacial acetic acid then isopropanol, followed by heating until red-hot with a propane torch. For DSC, all samples were hermetically sealed in aluminium pans. All samples were heated beyond the point of complete volatilization with a ramp rate of 10 °C / min, using nitrogen (99.998% purity, 50 seem) as the purge gas. Decomposition temperatures (TD) were determined as the onset of an exothermic event. The melting points were measured as the onset of the endothermic process and were also verified using an ex situ melting point apparatus.

[0197] Example 3. Surface Preparation

[0198] Substrates were prepared starting from mechanical grade Si wafers coated with approximately 5 nm of chromium or titanium (for adhesion) followed by 100 nm of metal (Au, Ag, Cu) using a physical vapour deposition tool (Angstrom COVAP). Substates patterned with gold lines were prepared by photolithography using 100 pm wide photoresist mask with a liftoff process. An oxygen plasma was first used to clean the residual photoresist from the open areas of the wafer followed by the deposition of 5 nm of chromium or titanium for adhesion before the deposition of 100 nm of gold by magnetron sputtering. A schematic showing surface deposition of triazolium bicarbonate compounds on Au is shown in Fig. 1B.

[0199] The substrates were kept in the cleanroom under ambient conditions until the wafers were diced into rectangular coupons approximately 1 x 1 cm for use. All metal surfaces were handled using flame-annealed tweezers during cleaning and deposition procedures. Organic contaminants were removed from Au surfaces by either argon plasma clean for 5 minutes or by submerging in concentrated sulfuric acid at room temperature for 10 minutes, rinsing with DI water (3 x 2 mL) and MeOH (3 x2 mL) before drying under a stream of argon. Example 4. Solution Deposition Conditions for Gold on Silicon

[0200] The clean coupons were submerged in a 10 mM solution of triazolium bicarbonate salt and methanol for 48 h. After 48 h the coupons were removed from the solutions and dried under a stream of argon.

[0201] Example 5A. Vapour Deposition Conditions on Gold on Mica

[0202] Vapour depositions were completed by adhering freshly cleaned surfaces to a cold finger of a sublimation apparatus using double-sided tape. The sublimation apparatus was then loaded with 10 mg of triazolylidenes, before attaching the cold finger and reducing the pressure to

[0203] 2 x 10'1Torr.

[0204] Vapour deposition was achieved by heating solid triazolylidenes to 150 °C for 10 minutes under static vacuum while in the presence of Au, Ag or Cu substrates. After cooling to room temperature, the substrates were rinsed with hexanes (3 x2 mL) before drying under argon.

[0205] Example 5B. Atomic Layer Deposition of TzDipp

[0206] To assess surface modification, a precursor (TzDipp«HCO3)(see Table 1 for structural formula) was used to perform deposition of 1,3-Bis(2,6-diisopropylphenyl)-1,2,3-triazol-5-ylidene. This deposition was conducted on (i) gold (Au) coated wafers, and (ii) patterned Au and SiO2 wafers. The depositions were conducted using an atomic layer deposition reactor. The temperature of the TzDipp«HCO3 precursor was maintained at 145°C, while the chamber temperature was set to 150°C. The chamber was evacuated to a pressure of 12 mTorr before dosing with TzDippin gaseous form. During pulsing and soaking TzDipp, the chamber pressure was increased up to 6000 mTorr over a 10 second period. During a final purging step, the chamber was supplied with a nitrogen atmosphere.

[0207] In regard to the deposition on Au wafers, a high resolution XPS spectrum for TzDippon Au showed signals of C 1s and N 1s (see Fig. 8). These XPS results confirmed that TzDippwas successfully deposited by vapor phase onto Au in the ALD chamber.

[0208] In regard to the deposition on patterned Au / SiO2 wafers, ToF-SIMS mapping ion intensity for Au (m / z: 197) and TzDipp(m / z: 320) (see Fig. 9) confirmed that TzDippwas selectively deposited on the Au bands of the patterned Au and SiO2 wafer. Substantially no TzDippdeposited on the SiO2 bands of the patterned wafer. Example 6. XPS Analysis

[0209] Control treatment of Au surfaces included MeOH, 50 °C, 24h. XPS analysis was conducted for blank Au surfaces. Results are shown in Table 3.

[0210] Survey XPS measurements of a blank gold surface indicated the presence of Au (54 %), C (37 %), O (6 %), Cu (2 %) and I (0.5 %). Adventitious carbon and oxygen contaminants are expected from handling gold under ambient conditions, while copper and iodide contaminants likely originate from sample handling and / or storage. High resolution XPS measurements were obtained for the C 1s, N 1s, O 1s and Au 4f regions. Further support for adventitious carbon contaminants was obtained from the C 1s and O 1s regions, which indicated the presence of organic oxides (esters, ketones). Small amounts of amides were also found based on N 1s XPS analysis. The results are summarized in Table 3.

[0211] Example 7. Thermal annealing studies of Triazolylidenes on Au

[0212] Desorption studies examined the thermal stability of Tz monolayers on gold surfaces by subjecting individual samples to a controlled heat treatment ranging from 150°C to 200°C in a vacuum oven, each for a duration of one hour. This approach was designed to determine the critical desorption temperature at which triazolylidenes detach from the gold substrate (Tmax). M+ions were calculated to be a percentage of the M+intensity of the parent Tz deposition by ToF-SIMS.

[0213] Example 8. Chemical stability tests of Tz-functionalized Au surfaces

[0214] ToF-SIMS spectra for TzlPr,lPr, TzlPr, and TzBnon Au were conducted after treatment with 1 % H2O2, pH 2, and pH 12 solutions. These TOF-SIMS spectra verified that even after exposure to these solutions for 48h, the Tz free carbene was still present on the surface.

[0215] Example 9A. Area-Selective Atomic Layer Deposition of ZnO

[0216] TzDipp, TzlPr,lPr, and TzlPrwere deposited on Au-patterned silicon wafers ~100nm thick and 100 pm apart by chemical vapour deposition (CVD). Coupons were loaded in a custom ALD reactor at 150 °C under a -4.20 x10'1Torr vacuum and N2 carrier gas at 100 seem. ZnO was then deposited using ZnEt2and H2O, with both bubblers at room temperature, and sequentially pulsed for 2.5 s and 1 s, respectively, with 60 s purges for 500 cycles. The samples were coated with -4 nm of Ir by sputtering for microscopy. EDS showed the concentrations of Zn on Tz-protected Au regions were significantly less and negligible compared to the concentrations of Zn observed on SiO2 regions. This result indicated that inhibition of ZnO growth on Tz-protected Au regions was successful. Example 9B. Dielectric Area-Selective Atomic Layer Deposition (AS-ALD)

[0217] HfC>2 Deposition Method

[0218] The HfO2 ALD process was developed as a dielectric material by using a precursor of tetrakis(ethylmethylamino)hafnium (TEMAHf) and water. The deposition temperature was about 200 °C, providing a growth rate of 1.4 A / cycle.

[0219] Referring to Fig. 10A, an SEM image shows two separated areas as the brighter region was Tz-coated Au metal while darker region was SiC>2. Scale bar is 1 urn = 1000 nm.

[0220] Referring to Fig. 10B, an EDX spectrum shows results of scanning the region of interest for TzDippon the Au area versus on the SiC>2 area. In the EDX spectrum, the Hf peak was exclusively on the SiC^area. This result demonstrated that in very small scale (range in nm) HfC>2 was selectively deposited on SiC>2.

[0221] Fig. 4F shows SEM and EDS element mapping for HfC>2 AS-ALD at deposition temperature of 200 °C for 100 cycles, wherein Si, Hf, and C elements represented SiC>2, HfC>2, and TzDipp, respectively, and a scale bar was 100 urn.

[0222] These results have clearly demonstrated that large scale (range in urn) HfC>2 was selectively deposited on SiC>2. The effect of TzDippsurface modification effectively suppressed HfC>2 nucleation on metal Au surfaces, enabling highly selective deposition on SiC>2 regions.

[0223] Example 9C. AS-ALD on Cu, Ru, and Co

[0224] Performance of AS-ALD was also studied on metal band / dielectric band patterned wafers that had metals that are more reactive than gold. The patterned wafers were Cu / SiC>2, Ru / SiC>2, and Co / SiCk. To facilitate the deposition of Tz molecules onto the metal bands of these wafers, a preliminary surface cleaning step was introduced to remove a thin native oxide layer that typically forms on reactive metals. H2 / Ar plasma treatment was conducted using a Meaglow hollow cathode plasma generator operated at 150 W for 60 seconds, with the chamber maintained at 150 °C. After the cleaning step, the patterned wafers were subjected to TzDippdeposition followed by HfC>2 AS-ALD conditions as described above in Example 5B and 9B. The resulting films were analyzed by SEM and EDS to evaluate the inhibition performance of the TzDipplayer (see Fig. 4F).

[0225] Characterization

[0226] The area-selective adsorption of TzDippon reactive metal / SiO2patterned sample was characterized by ToF-SIMS. As shown in the TOF-SIMS ion intensity mapping for Cu, Co, and Ru pattern of Fig. 4D, the ion mapping revealed clear compositional contrasts corresponding to metal and dielectric regions. The TzDipplayer was distinctly localized on the metal bands while the SIO2regions remained free of TzDippdeposition, indicating strong selectivity. The ions were collected in negative or positive mode where m / z for Cu: 63; Ru: 102; Co: 59; TzDipp: 320.

[0227] This study showed that TzDipphas high selectivity for Cu, Ru, and Co. In addition, HfO2 exhibited selectivity for the dielectric bands over the TzDipp-protected metal bands. See Fig. 4D to 4F for TOF-SIMS ion mapping images which demonstrate this high selectivity of TzDippfor the metal bands and the HfO2 selective deposition on the SiO2 dielectric bands.

[0228] EQUIVALENTS

[0229] It will be understood by those skilled in the art that this description is made with reference to certain embodiments and that it is possible to make other embodiments employing the principles of the invention which fall within its spirit and scope.

[0230] Table 1. Structural Formulae of 1,2,3-triazolium salts and 1,2,3-triazol-5-ylidenes

[0231]

[0232] 1 -[2,6-Bis( 1 -methylethyl)phenyl]-3- methyl-4-phenyl-1 A7-1,2,3-triazolium- bicarbonate (TzDipp*H2CO3)

[0233] 1 -[2,6-Bis( 1 -methylethyl)phenyl]-3- methyl-4-phenyl-1 A7-1,2,3-triazolium- TzDipp(as shown above) triflate (TzDipp«OTf)

[0234] TziPr. H2CO3

[0235] TzBn. H2CO3

[0236]

[0237]

[0238]

[0239] Table 2A. Energy dispersive spectrometer (EDS) measurement of TzlPr,lPrinhibited substrate at Au line region

[0240] Wt% Standard Deviation

[0241] Au 79.5 0.2

[0242] Zn 7.6 0.1

[0243] C 6.0 0.1

[0244] 0 4.0 0.1

[0245] Si 2.9 0.1

[0246]

[0247] Table 2B. Energy dispersive spectrometer (EDS) measurement of TzlPr,lPrinhibited substrate at dielectric line region

[0248] Wt% Standard Deviation

[0249] O 46.7 0.2

[0250] Si 39.4 0.2

[0251] Zn 7.9 0.1

[0252] C 5.5 0.2

[0253] Na 0.5 0.1

[0254]

[0255] Table 2C. Energy dispersive spectrometer (EDS) measurement of TzlPrinhibited substrate at Au line region

[0256] Wt% Standard Deviation

[0257] Au 89.1 0.2

[0258] C 6.5 0.2

[0259] Si 3.4 0.1

[0260] O 1.0 0.1

[0261]

[0262] Table 2D. Energy dispersive spectrometer (EDS) measurement of TzlPrinhibited substrate at dielectric line region

[0263] Wt% Standard Deviation

[0264] 0 39.4 0.2

[0265] Si 30.9 0.1

[0266] Zn 22.8 0.2

[0267] C 6.9 0.2

[0268]

[0269] Table 3. XPS data for blank Au Surfaces

[0270] Position (eV) Atomic % FWHM Identity Au 4f 84.5 28.7 0.71 metallic Au 88.2 21.5 0.71

[0271] C 1s 284.8 27.9 1.3 C-C, C-H 286.3 6.8 1.3 C-OH, C-O-C 287.6 2.2 1.3 C=O 289.0 2.5 1.3 O-C=O

[0272] N 1s 400.1 0.9 1.5 N-C=O

[0273] O 1s 532.0 7.4 1.5 O-(C=O*)-C, C=O 533.4 2.2 1.5 O*-(C=O)-C, H2O Table 4A. High-Res XPS data of TzDippon Au

[0274] Position (eV) Atomic % FWHM Identity Au 4f 83.6 37.5 0.72 metallic Au 87.3 29.3 0.72

[0275] C 1s 284.8 14.9 1.4 C-C, C-H 286.1 5.2 1.4 C-N, C-OH 287.0 2.7 1.4 C=O 288.7 1.0 1.4 O-C=O

[0276] N 1s 399.8 0.7 2.0 N-N*=N 401.8 1.4 2.0 N*-N=N*

[0277] O 1s 531.7 6.0 1.9 O-(C=O*)-C, C=O 533.0 1.3 1.9 O*-(C=O)-C, H2O

[0278] Table 4B. High-Res XPS spectra of TzlPr,lPron Au

[0279] Position (eV) Atomic % FWHM Identity Au 4f 83.3 32.6 0.69 metallic Au 87.0 25.2 0.69

[0280] C 1s 284.8 16.2 1.4 C-C, C-H 286.1 5.1 1.4 C-N, C-OH 287.1 1.5 1.4 C=O 288.8 1.1 1.4 O-C=O

[0281] N 1s 401.0 1.3 2.0 N-N*=N 401.9 2.6 2.0 N*-N=N*

[0282] O 1s 531.0 7.1 1.6 O-(C=O*)-C, C=O 532.3 7.0 1.6 O*-(C=O)-C, H2O

[0283] Table 4C. High-Res XPS spectra of TzMeon Au Position (eV) Atomic % FWHM Identity Au 4f 84.1 27.7 0.76 metallic Au 87.8 21.2 0.76

[0284] C 1s 284.7 28.8 1.4 C-C, C-H 286.0 6.0 1.4 C-N, C-OH 287.0 2.4 1.4 C=O 288.8 1.1 1.4 O-C=O

[0285] N 1s 400.5 1.1 1.4 N-N*=N 401.9 2.2 1.4 N*-N=N*

[0286] O 1s 530.6 8.1 1.6 O-(C=O*)-C, C=O 532.3 1.2 1.6 O*-(C=O)-C, H2O Table 4D. High-Res XPS spectra of TzEton Au

[0287] Position (eV) Atomic % FWHM Identity Au 4f 83.5 27.3 0.72 metallic Au 87.2 21.0 0.72

[0288] C 1s 284.7 19.2 1.4 C-C, C-H 286.0 6.0 1.4 C-N, C-OH 287.0 2.2 1.4 C=O 288.7 1.4 1.4 O-C=O

[0289] N 1s 401.1 0.9 1.9 N-N*=N 402.2 1.8 1.9 N*-N=N*

[0290] O 1s 530.6 11.7 1.6 O-(C=O*)-C, C=O 532.1 7.9 1.6 O*-(C=O)-C, H2O Table 4E. High-Res XPS spectra of TzlPron Au

[0291] Position (eV) Atomic % FWHM Identity Au 4f 84.2 18.1 0.67 metallic Au 87.9 13.9 0.67

[0292] C 1s 284.8 26.2 1.3 C-C, C-H 286.3 5.1 1.3 C-N, C-OH 287.1 1.8 1.3 C=O 288.8 1.1 1.3 O-C=O

[0293] N 1s 400.7 0.8 1.8 N-N*=N 402.3 1.6 1.8 N*-N=N*

[0294] O 1s 530.7 28.0 1.7 O-(C=O*)-C, C=O 532.4 2.9 1.7 O*-(C=O)-C, H2O Table 4F. High-Res XPS spectra of TzBnon Au

[0295] Position (eV) Atomic % FWHM Identity Au 4f 83.9 26.5 0.64 metallic Au 87.5 20.3 0.64

[0296] C 1s 284.7 31.1 1.3 C-C, C-H 286.1 7.0 1.3 C-N, C-OH 287.0 1.5 1.3 C=O 288.8 1.2 1.3 O-C=O

[0297] N 1s 399.7 0.6 1.6 N-N*=N 402.1 1.1 1.6 N*-N=N*

[0298] O 1s 531.3 2.0 1.6 O-(C=O*)-C, C=O 532.5 6.3 1.6 O*-(C=O)-C, H2O Table 5. Thermal Characterization Data of Tz compounds.

[0299] Compound Tv (°C) TD (°C) TD-TV (°C) Melting Point (°C) TziPr iPr. H2CO3136 >350 >214 123-125 TzDipp. H2CO3225 >600 >375 94-96 TzBn. H2CO3258 >350 >92 50-53 TzMe. H2CO3203 >450 >247 142-144 TzEt. H2CO3199 >350 >151 128-130 TziPr. H2CO3205 >450 >245 124-126

[0300]

[0301] Tv is temperature of volatilization; TD is temperature of decomposition; and TD-TVis the thermal window between the temperature of decomposition and the temperature of volatilization.

Claims

We claim:

1. A compound having a structure as shown:TzBn,3-benzyl-1 -undecyl-4-nonyl-1 A7-1,2,3- triazolidene,1-(4-bromobenzyl)-3-methyl-4-phenyl-1 / - / -1,2,3- triazolidene,1, 3,4-tri isopropyl- 1 H-1,2,3-triazolidene,1 -(2,6-diisopropylphenyl)-3-nonyl-4-phenyl-1 H- 1,2,3-triazolidene,or a hydrated or solvated form thereof,where X is an anion.

2. The compound of claim 1, wherein X is hydroxide, alkoxide, halide, HCO3⁻, or triflate.

3. A method of selective deposition, comprising:disposing a substrate, which comprises a metal surface, or which comprises both metal and non-metal or metal oxide, in a deposition chamber, which comprises a valve-controlled inlet for a carrier gas and a furnace, wherein the carrier gas has valve-controlled access to a bubbler that houses a 1,2,3-triazolium salt of Formula 1, a carboxylate zwitterion form of 1,2,3-triazole, or hydrated or solvated forms thereof;heating and maintaining the bubbler at a sufficiently high temperature to generate gaseous free 1,2,3-triazol-5-ylidene of Formula 2, that moves into the deposition chamber and selectively chemisorbs onto the metal surface, wherein substantially no 1,2,3-triazol-5-ylidene chemisorbs onto the non-metal or metal oxide surface(1) (2)where X is an anion;R3is a substituted or unsubstituted C1-C10 aliphatic moiety;R1and R2are independently a substituted or unsubstituted Ci to C12 alkyl, alkenyl, or alkynyl group that is linear, branched, or cyclic, a substituted or unsubstituted aromatic moiety, or a combination thereof, wherein a substituent comprises an alkyl, alkenyl, alkynyl, halo, heteroatom, and optionally two of R1, R2, and R3are joined in a cyclic structure, wherein at least one of R1and R2is an aryl moiety, an aliphatic cyclic moiety, or a heterocyclic moiety.

4. The method of claim 3, wherein X is hydroxide, alkoxide, halide, HCO3⁻, or triflate.

5. A method of deposition, comprising:disposing a substrate in a deposition chamber, wherein the substrate comprises at least a metal surface, and wherein the deposition chamber comprises a valve-controlled inlet for a carrier gas, and wherein the carrier gas has valve-controlled access to a bubbler that contains 1,2,3-triazolium salt, a carboxylate zwitterion form of 1,2,3-triazole, or hydrated or solvated forms thereof of claim 3;heating and maintaining the bubbler at a sufficiently high temperature to generategaseous free 1,2,3-triazol-5-ylidene of claim 3 or a hydrated or solvated form thereof, that moves into the deposition chamber where 1,2,3-triazol-5-ylidene, or a hydrated or solvated form thereof, chemisorbs onto the metal surface.

6. The method of any one of claim 3 to 5, further comprising intermittently pulsing carrier gas that includes gaseous 1,2,3-triazol-5-ylidene into the deposition chamber and purging the deposition chamber with carrier gas.

7. A method of solution-phase selective deposition, comprising:immersing a substrate, which comprises a metal surface, and a non-metal or metal oxide surface, in a container, which comprises a solution comprising 1,2,3-triazolium salt of Formula 1 of claim 3, or a carboxylate zwitterion form of 1,2,3-triazole; andallowing 1,2,3-triazol-5-ylidene of Formula 2 of claim 3 to deposit on the metal surface;wherein the 1,2,3-triazol-5-ylidene selectively chemisorbs onto the metal surface, and substantially no 1,2,3-triazol-5-ylidene chemisorbs onto the non-metal or metal oxide surfacewhere X is an anion;where R3is a substituted or unsubstituted Ci-C aliphatic moiety;R1and R2are independently a substituted or unsubstituted Ci to C12 alkyl, alkenyl, or alkynyl group that is linear, branched, or cyclic, a substituted or unsubstituted aromatic moiety, or a combination thereof, wherein a substituent comprises an alkyl, alkenyl, alkynyl, halo, heteroatom, and optionally two of R1, R2, and R3are joined in a cyclic structure, wherein at least one of R1and R2is an aryl moiety, an aliphatic cyclic moiety, or a heterocyclic moiety.

8. The method of claim 7, where X is hydroxide, alkoxide, halide, HCOs", or triflate.

9. The method of any one of claims 3 to 8, wherein the substrate is a patterned substrate having a metal surface adjacent to a dielectric surface.

10. The method of any one of claims 3 to 9, wherein R3is methyl.

11. The method of any one of claims 3 to 9, wherein R2is phenyl.

12. The method of any one of claims 3 to 11, wherein the pulsing is opening the gas inlet valve for a selected time for a selected number of cycles.

13. The method of claim 12, wherein the number of cycles is about 100.

14. The method of any one of claims 3 to 13, wherein the metal surface is thick enough to exhibit bulk properties.

15. The method of any one of claims 3 to 14, wherein the metal surface is between 0.5 to 1 000 nm thick.

16. The method of claim 15, wherein the metal surface is between 25 and 150 nm thick.

17. The method of claim 15, wherein the metal surface is about 100 nm thick.

18. The method of any one of claims 3 to 17, wherein the selected deposition temperature is in a range of about room temperature to about 500 °C.

19. The method of claim 18, wherein the selected deposition temperature is in a range of about 30 to about 200°C.

20. The method of any one of claims 3 to 19, wherein the deposition chamber is suitable for holding wafers.

21. The method of any one of claims 3 to 20, wherein the deposition chamber is suitable for sustaining a vacuum in a range of about 0.1 torr to about 5 torr.

22. The method of claim 21, wherein the deposition chamber is suitable for sustaining a vacuum of about 3 torr.

23. The method of any one of claims 3 to 22, wherein the carrier gas is nitrogen or argon.

24. The method of any one of claims 3 to 23, wherein the purging the deposition chamber with carrier gas is performed for about 20 seconds.

25. The method of any one of claims 3 to 24, wherein the 1,2,3-triazol-5-ylidene chemisorbs onto the metal surface as a monolayer.

26. The method of any one of claims 3 to 25, wherein the 1,2,3-triazol-5-ylidene chemisorbs onto the metal surface as a bilayer.

27. The method of any one of claims 3 to 25, wherein the 1,2,3-triazol-5-ylidene chemisorbs onto the metal surface as a multilayer.

28. The method of any one of claims 3 to 27, further comprising cooling the deposition chamber to room temperature while continuously purging the deposition chamber with carrier gas.

29. The method of any one of claims 3 to 28, wherein the non-metal or metal oxide surface is a dielectric surface.

30. The method of claim 29, wherein the non-metal or metal oxide surface comprises ZnO, SiC>2, Si3N4, HfC>2, WO3, AI2O3, SiwOzNywherein w is 0 to 3, z is 0 to 2 and y is 0 to 4, HfC, or any combination thereof.

31. The method of any one of claims 3 to 30, further comprising removal of the 1,2,3-triazol-5-ylidene by thermal desorption to regenerate a pristine metal surface.

32. The method of any one of claims 3 to 31, wherein the 1,2,3-triazol-5-ylidene is1-(4-bromobenzyl)-3-methyl-4-phenyl-1 / - / - 1,2,3-triazolidene,-benzyl-1-undecyl-4-nonyl-1 / - / -1,2,3- triazolidene,1, 3,4-tri isopropyl- 1 H-1,2,3-triazolidene, or1-(2,6-diisopropylphenyl)-3-nonyl-4-phenyl- 1 H-1,2,3-triazolidene,or a hydrated or solvated form thereof.

33. The method of any one of claims 3 to 32, wherein the metal surface of the substrate comprises Au, Cu, Ag, Ru, W, Ni, Fe, Mo, Co, Pt, Pd, or an alloy.

34. The method of any one of claims 3 to 33, further comprising a step of treating the substrate to refine the interface between the metal surfaces, and the non-metal or metal oxide surfaces.

35. The method of claim 34, wherein the treating the substrate comprises thermal annealing or plasma treatment.

36. The method of any one of claims 3 to 35, wherein the 1,2,3-triazolium salt is®OTf1 -[2,6-Bis( 1 -methylethyl)phenyl]-3-methyl-4- phenyl-1 H-1,2,3-triazolium-triflate(TzDipp«OTf),3-benzyl-1 -undecyl-4-nonyl-1 A7-1,2,3-triazol- 3-ium bicarbonate,1-(4-bromobenzyl)-3-methyl-4-phenyl-1 / - / - 1,2,3-triazol-3-ium bicarbonate,1, 3,4-tri isopropyl- 1 H-1,2,3-triazol-3-ium1-(2,6-diisopropylphenyl)-3-nonyl-4-phenyl- 1H-1,2,3-triazol-3-ium bicarbonate, or hydrated or solvated forms thereof.

37. The method of any one of claims 3 to 36, further comprising cleaning the substrate prior to the deposition of 1,2,3-triazol-5-ylidene.

38. The method of claim 37, wherein the cleaning the metal surface comprises exposing it to hot plasma.

39. The method of claim 38, wherein the hot plasma is a plasma of H2at about 400°C.

40. The method of any one of claims 37 to 39, further comprising modifying the temperature of the deposition chamber to a selected deposition temperature if the deposition temperature differs from a temperature of cleaning.

41. The method of any one of claims 3 to 40, further comprising evacuating the deposition chamber such that it is under vacuum prior to the deposition of 1,2,3-triazol-5-ylidene.

42. The method of any one of claims 3 to 41, further comprising annealing the substrate after 1,2,3-triazol-5-ylidene deposition.

43. Use of a salt of Formula 1 or a carboxylate zwitterion form thereof, for generation of gaseous free 1,2,3-triazol-5-ylidene of Formula 2 for deposition onto a metal surface(1)where X is an anion;R3is a substituted or unsubstituted C1-C10 aliphatic moiety;R1and R2are independently a substituted or unsubstituted Ci to C12 alkyl, alkenyl, or alkynyl group that is linear, branched, or cyclic, a substituted or unsubstituted aromatic moiety, or a combination thereof, wherein a substituent comprises an alkyl, alkenyl, alkynyl, halo, heteroatom, and optionally two of R1, R2, and R3are joined in a cyclic structure, wherein at least one of R1and R2is an aryl moiety.

44. The use of claim 43, wherein X is hydroxide, alkoxide, halide, HCO3⁻, or triflate.

45. The use of claim 43 or 44, wherein R3is methyl.

46. The use of any one of claims 43 to 45, wherein R2is phenyl.

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