Method of depositing molybdenum or tungsten material

Abstract

The invention provides a method for the rapid deposition of highly conformal molybdenum or tungsten containing films onto microelectronic device substrates under vapor deposition conditions. In the practice of the invention, a first nucleation step is performed while using a generally lower concentration of metal precursor than is typically used in the reaction zone. The use of this lower concentration of metal precursor can be achieved by adjusting the temperature of the ampoule (which contains the precursor), the concentration of the precursor, the pressure in the reaction zone, and the duration of the pulse. In this manner, a generally lower concentration is used to form a nucleation layer greater than or equal to about or up to about 9, 15, or 20 A, at which point the conditions under which the precursor is introduced can be advantageously changed and the concentration of the precursor in the reaction zone increased for the purpose of bulk deposition.

Description

Technical Field

[0001] This invention relates to the vapor deposition of molybdenum or tungsten-containing materials onto microelectronic substrates. Background Technology

[0002] Molybdenum and tungsten are increasingly used in the manufacture of semiconductor devices due to their extremely high melting points, low coefficients of thermal expansion, low resistivity, and high thermal conductivity, including for diffusion masks, electrodes, photomasks, power electronic substrates, low resistivity gates, and interconnects.

[0003] Such utility has spurred efforts to achieve the deposition of molybdenum and tungsten films for applications characterized by high conformability and high deposition rates suitable for efficient, high-volume manufacturing operations. This, in turn, has prompted efforts to develop improved molybdenum and tungsten source reagents for vapor deposition operations, and improved process parameters utilizing such reagents. Furthermore, difficulties are often encountered when depositing molybdenum onto certain substrates, such as metals, metal nitrides, dielectrics (oxides), semiconductors, and superconductors, because deposition delays can often be associated with the difficulty of establishing nuclei on the substrate surface before the required layer-by-layer deposition. As deposition temperatures decrease, the overall deposition rate typically decreases, and the sensitivity to various substrate surfaces generally becomes more pronounced.

[0004] There is still a need to achieve higher deposition rates for molybdenum and tungsten materials to accommodate efficient, high-volume manufacturing operations. Summary of the Invention

[0005] In some embodiments, the present invention provides a method for rapidly depositing highly conformal, metal-containing (e.g., molybdenum- and tungsten-containing films) onto a microelectronic device under vapor deposition conditions at reduced temperatures (i.e., below about 400°C), thereby enabling the deposition method to be used in a wider range of integration schemes, including logic device fabrication. In practice, a first nucleation step is performed while using a metal precursor concentration that is generally lower than that typically present in the reaction zone. This lower concentration can be achieved by adjusting the temperature of the ampoule (containing the precursor), the precursor concentration, the pressure in the reaction zone, and the duration of the pulse. In this way, a generally lower concentration is used to form a film greater than or equal to about 3 angstroms. Or at most about 9, 15 or In this nucleation layer, it is advantageous to change the conditions for introducing the precursor and increase the concentration of the precursor in the reaction zone to achieve bulk deposition (e.g., more than 50% higher than the concentration used in the nucleation step). In one embodiment, a molybdenum precursor, such as MoO2Cl2, is used to deposit a molybdenum-containing film onto a titanium nitride surface, although the method is considered broadly applicable to depositing molybdenum- or tungsten-containing films onto surfaces where it is difficult to form a metal nucleation layer (i.e., nucleation delay is often encountered), such as metals, metal nitrides, dielectric materials (oxides), semiconductors, and superconductors. Attached Figure Description

[0006] Figure 1 To prepare Mo with MoO2Cl2 as a precursor via chemical vapor deposition (CVD) Scanning electron micrograph (SEM) of the nominal bare titanium nitride surface with Mo mass equivalent thickness. Substrate temperature: 450 °C.

[0007] Figure 2 SEM image of a (comparative) example of molybdenum chemical vapor deposition on titanium nitride using MoO2Cl2 at a substrate temperature of 400°C. This example shows a surface mass equivalent thickness of [missing information]. Poor nucleation at Mo, where only the molybdenum oxide phase is visible by X-ray diffraction.

[0008] Figure 3 This is a SEM image demonstrating the deposition / nucleation of molybdenum on a titanium nitride substrate using the method of this invention (and a substrate temperature of 390°C). The Mo film has... The mass equivalent thickness. (See Example 1 below).

[0009] Figure 4 SEM images of a membrane prepared using nucleation step conditions, which are used to extend the number of cycles to produce a slightly thicker Mo film on the via structure to demonstrate the good shape retention of the membrane.

[0010] Figure 5 For deposited on PVD Mo substrates with SEM images of Mo films with mass equivalent thickness. CVD conditions: T sub =390℃, low precursor concentration 30ppm. This data shows that the PVD Mo substrate is a starting surface comparable to the Mo nucleation step before bulk Mo deposition.

[0011] Figure 6 For deposited on TiN substrates by CVD, having SEM images of Mo films with mass equivalent thickness. Deposition conditions: T sub =450℃, precursor concentration =37ppm. This is close to the lower limit of the substrate temperature, where this concentration allows Mo to be deposited on TiN.

[0012] Figure 7 This is a SEM image of the Mo film deposited on the TiN substrate in step 2. The mass-equivalent thickness of Mo is... The deposition temperature is T sub =390℃; pulsed CVD nucleation layer uses a low precursor concentration of 22 ppm; bulk CVD deposition uses a precursor concentration of 30 ppm. This data demonstrates that the Mo nucleation step produces a starting surface suitable for bulk Mo deposition (comparable to PVD Mo substrates).

[0013] Figure 8 For A graph showing TiN etching versus H2 flow rate (sccm). This data demonstrates that increasing the H2 flow rate reduces the precursor concentration and shows how reducing the concentration during the nucleation step can reduce substrate (TiN) etching.

[0014] Figure 9 A comparison of CVD molybdenum deposition rates on titanium nitride and PVD molybdenum substrates as a function of deposition time. Substrate temperature = 650 °C, pressure = 80 Torr, argon carrier gas flow rate = 50 sccm, hydrogen co-reactant gas flow rate = 4000 sccm. The figure illustrates the effect of nucleation delay on deposition rate. The figure also shows that, compared to TiN substrates, the molybdenum deposition rate on titanium nitride substrates increased by at least 25% in the 300-600 second time period. Precursor concentration = 20 ppm. Detailed Implementation

[0015] As used in this specification and the appended claims, unless the context clearly indicates otherwise, the singular forms “a / an” and “the” include a plural of indicators. As used in this specification and the appended claims, unless the context clearly indicates otherwise, the term “or” is generally used in its meaning as including “and / or”.

[0016] The term "approximately" typically refers to a range of numerical values ​​that are considered equivalent to the value (e.g., having the same function or result). In many cases, the term "approximately" may include a numerical value rounded to the nearest significant number.

[0017] The range of values ​​expressed using endpoints includes all values ​​contained within the range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0018] Generally speaking, the deposition method of the present invention involves the deposition of approximately to approximately The formation of a metal nucleation layer is performed as the first step. This first step is advantageously carried out in the reaction zone at a relatively low precursor concentration compared to the precursor concentration used thereafter, i.e., in forming the bulk film. Generally, using a first, lower concentration of precursor to form the nucleation layer improves the overall processing time for film deposition to the final desired thickness, and it has been unexpectedly found that the lower precursor concentration reduces nucleation delay, which is typically seen in the case of molybdenum and tungsten precursors on certain substrates. This relatively low concentration of precursor in the reaction zone is, in one embodiment, about 1 mol% to about 75 mol%, or about 10 mol% to about 50 mol%, of the concentration used in the bulk deposition step. All proportions and concentrations listed herein are in moles.

[0019] Therefore, in a first aspect, the present invention provides a method for vapor-phase deposition of a molybdenum or tungsten-containing film onto the surface of a microelectronic device, comprising introducing a molybdenum or tungsten precursor and a reducing gas into a reaction zone containing the surface, wherein the precursor has a first precursor concentration in the reaction zone until a concentration of approximately [missing information] has been deposited. to approximately A film of desired thickness is formed, and then a molybdenum or tungsten precursor and a reducing gas are introduced into the reaction zone, wherein the precursor has a second precursor concentration in the reaction zone until a molybdenum or tungsten film of desired thickness is deposited, and wherein the first precursor concentration is about 1% to about 75% of the second precursor concentration.

[0020] As those skilled in the art will understand, after the invention recognizes that the precursor concentration is relatively low in the first stage of deposition (to form a nucleation layer), followed by the second stage of deposition of the majority of the film, the invention can be practiced in several ways, such as pulsed introduction of the precursor and continuous introduction of the reducing gas, continuous introduction of the precursor and continuous introduction of the reducing gas, and tandem pulsed introduction of both the precursor and the reducing gas, with or without an intermediate rinsing step using an inert gas. Therefore, other arrangements of these individual schemes are conceivable, as long as the concentration in the first (nucleation) stage is relatively lower than that used in subsequent stages where the majority of the film is deposited on the surface of the microelectronic device. Furthermore, those skilled in the art, when selecting a particular precursor over another, will first consider the vapor pressure of the precursor, then the specific tools used in the deposition method and the configuration and volume of its accompanying reaction zone, and then adjust the pressure, concentration, and flow rate of the specific precursor and / or any carrier gas used to achieve the target precursor concentration for each of the two stages mentioned herein.

[0021] In a second aspect, the present invention provides a method for vapor-phase deposition of a molybdenum- or tungsten-containing film onto a surface of a microelectronic device in a reaction zone operated at a pressure of about 1 Torr to about 1000 Torr and a temperature of about 300°C to about 1000°C; wherein the surface is selected from nitrides, oxides, metals, semiconductors, and superconductors, and the method comprises:

[0022] a. A molybdenum or tungsten precursor is repeatedly introduced in pulses into a reaction zone containing a surface for a duration of approximately 0.1 seconds to approximately 120 seconds, followed by a pause of approximately 1 second to approximately 120 seconds, wherein the initial concentration of the precursor in the reaction zone is approximately 1 ppm to approximately 5000 ppm at its peak, while a reducing gas is continuously introduced into the reaction zone until a surface has been deposited with approximately to approximately Thickness of the film, and

[0023] b. A molybdenum or tungsten precursor is repeatedly introduced in a pulsed manner into the surface-containing reaction zone for a duration of about 0.1 seconds to about 120 seconds to reach a second precursor concentration, followed by a pause of about 1 second to about 120 seconds; wherein the second concentration of the precursor in the reaction zone is about 1.3 times to about 100 times the first precursor concentration, while a reducing gas is continuously introduced into the reaction zone until a film of the desired thickness has been deposited.

[0024] In a third aspect, the present invention provides a method for vapor-phase deposition of a molybdenum- or tungsten-containing film onto a surface of a microelectronic device in a reaction zone, said reaction zone being operated at a pressure of about 1 Torr to about 1000 Torr and a temperature of about 300°C to about 1000°C; wherein said surface is selected from nitrides, oxides, metals, semiconductors, and superconductors, and said method comprises:

[0025] a. A molybdenum or tungsten precursor is continuously introduced into a reaction zone containing a surface, wherein the initial concentration of the precursor in the reaction zone is from about 1 ppm to about 5000 ppm at its peak, while a reducing gas is continuously introduced into the reaction zone until a surface has been deposited with approximately to approximately Thickness of the film, and

[0026] b. A molybdenum or tungsten precursor is continuously introduced into a reaction zone containing a surface to achieve a second precursor concentration, wherein the second concentration of the precursor in the reaction zone is about 1.3 to about 100 times the first precursor concentration, while a reducing gas is continuously introduced into the reaction zone until a film of the desired thickness has been deposited.

[0027] In a fourth aspect, the present invention provides a method for vapor-phase deposition of a molybdenum- or tungsten-containing film onto a surface of a microelectronic device in a reaction zone, said reaction zone being operated at a pressure of about 1 Torr to about 1000 Torr and a temperature of about 300°C to about 1000°C; wherein said surface is selected from nitrides, oxides, metals, semiconductors, and superconductors, and said method comprises:

[0028] a. A molybdenum or tungsten precursor is repeatedly introduced into the surface-containing reaction zone for a first pulse duration of about 0.1 seconds to about 120 seconds, thereby achieving a first concentration of the precursor in the reaction zone, wherein the first concentration of the precursor in the reaction zone is about 1 ppm to about 5,000 ppm, and the reaction zone is flushed with an inert gas for about 1 second to about 120 seconds. A reducing gas is introduced into the reaction zone for a second pulse duration of about 0.1 seconds to about 120 seconds, and flushed with an inert gas for a duration of about 1 second to about 120 seconds, until a surface concentration of about [missing value] has been deposited. to approximately Thickness of the film, and

[0029] b. During a first pulse duration of about 0.1 seconds to about 120 seconds, a molybdenum or tungsten precursor is repeatedly introduced into the surface-containing reaction zone, thereby achieving a second precursor concentration in the reaction zone, wherein the second precursor concentration in the reaction zone is about 1.3 times to about 100 times the first concentration, and the reaction zone is flushed with an inert gas for about 1 second to about 120 seconds, and a reducing gas is introduced into the reaction zone during a second pulse duration of about 0.1 seconds to about 120 seconds, and flushed with an inert gas for a duration of about 1 second to about 120 seconds, until a film of the desired thickness has been deposited.

[0030] In the first to fourth aspects of the invention, various alternative embodiments are contemplated. In one embodiment, the concentration of the precursor in the nucleation (i.e., first) stage will be from about 1 ppm to about 5000 ppm, from about 10 ppm to about 2000 ppm, or from about 20 ppm to about 500 ppm.

[0031] In another embodiment, the concentration of the first precursor is about 10 mol% to about 50 mol% of the concentration of the second precursor.

[0032] In some embodiments, the pressure maintained in the reaction zone is about 1 to about 1,000 tor, about 20 to about 200 tor, or about 40 to about 120 tor.

[0033] In some embodiments, the temperature of the reaction zone is about 300°C to 1000°C, about 325°C to about 700°C, or about 350°C to 500°C.

[0034] In one embodiment, the surface is selected from nitrides, oxides, metals, semiconductors, and superconductors. Specific examples include silicon, SiO2, Si3N4, OSG, FSG, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, photoresist, hard photomask, carbon, germanium, germanium-containing, boron-containing, Ga / As, porous inorganic materials, metals such as copper and aluminum, and diffusion mask layers such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. In another embodiment, the surface is titanium nitride.

[0035] In another embodiment, the molybdenum and tungsten precursors are selected from WCl6, WCl5, WOCl4, MoO2Cl2, MoCl5, and MoOCl4. In another embodiment, the precursor is MoO2Cl2.

[0036] In another embodiment, when a pulse is introduced using the precursor, the pulse “on” time will be about 0.1 seconds to about 120 seconds, about 0.5 seconds to about 60 seconds, or about 0.5 seconds to about 3 seconds. The pulse pause (i.e., “off” time) can be about 1 second to about 120 seconds, about 20 seconds to about 60 seconds, or about 15 seconds to about 40 seconds.

[0037] As an example of the second aspect above, when using MoO2Cl2 as a precursor to deposit a molybdenum-containing film, the specified levels of these precursor concentrations can be achieved by using a step in which a predetermined amount of precursor is placed in an ampoule, the ampoule is heated to a predetermined temperature to fill the top space with a certain partial pressure of precursor vapor, the precursor vapor and carrier gas are then released into the reaction zone, and the introduction of additional precursor is then paused. Throughout this first step, at least one reducing gas is continuously introduced into the reaction zone. Additionally, during this pause, the carrier gas continues to flow into the ampoule, increasing the pressure within the ampoule while also effectively reducing the relative concentration within the ampoule. In this first step, the ampoule temperature can be maintained, for example, at a temperature of about 40°C to about 70°C, and the temperature of the reaction zone can be maintained at about 300°C to about 1000°C, or about 325°C to about 700°C, or about 350°C to about 500°C. Generally, during this example of the first step, the method is carried out in such a manner that the concentration of the precursor in the reaction zone is from about 1 ppm to about 5000 ppm. This concentration can be calculated as the partial pressure of the precursor vapor relative to the carrier gas and then further diluted by the reducing gas and any other gas in the chamber.

[0038] Once this nucleation layer is completed, approximately to approximately about to approximately or about to approximately Bulk deposition of a molybdenum-containing film can then be performed at relatively high concentrations, approximately 1.3 to 100 times higher than during the nucleation step. Since a nucleation layer has already been formed in the first step, bulk deposition can be performed much faster, allowing for the use of higher concentrations of precursor vapor. This method is particularly advantageous for metal precursor / substrate combinations that tend to exhibit delayed nucleation, such as oxide and nitride substrates. In the second step, where bulk deposition of a metal-containing film is performed, the introduction of the precursor into the reaction zone can be either continuous or pulsed. Generally, for this bulk deposition stage, in the case of continuous precursor inflow into the reaction zone, the precursor concentration in the reaction zone is maintained at approximately 1.3 to 100 times higher. In the case of pulsed introduction of the precursor into the reaction zone, the concentration will vary from approximately 1 ppm to approximately 5000 ppm depending on the flow rate and duration of the pulse during precursor introduction into the reaction zone. In either case, the concentration of the precursor in the reaction zone during this volumetric deposition will be approximately 1.3 to approximately 100 times (x / times) the concentration used in the first (nucleation) step, with the concentrations listed during such pulses reflecting the peak concentrations achieved during such pulses.

[0039] The utilization of the carrier gas and its flow rate will ultimately depend on the configuration of the deposition tool, the scale of its operation, and the specific precursors used.

[0040] The minimum thickness of a continuous monolayer observed is approximately In one embodiment, deposition continues until a thicker film is obtained to provide a continuous nucleation layer containing tungsten or molybdenum, for example, approximately or This enables further vapor deposition, ultimately providing a tungsten- or molybdenum-containing film of the desired thickness. It has been found that molybdenum-containing films are highly conformal, and in one case, in… The film has a resistivity of 37 μΩ-cm at its thickness. In one embodiment, the film exhibits a resistivity of about 10 μΩ-cm to about 1000 μΩ-cm.

[0041] The bulk deposition mentioned above can therefore be used to achieve approximately [a certain number of] pulse cycles per pulse. to approximately The deposition rate provides most of the film formation. Therefore, although the inventive technique using precursors with relatively low concentrations in the initial stages yields a high-quality, conformal nucleation layer, bulk deposition, whether in pulsed or continuous mode, can thus provide layer-by-layer deposition of molybdenum or tungsten films, allowing the entire method to achieve the desired final film thickness, for example, approximately [missing information - likely a specific thickness]. From approximately 5 micrometers, all of the above can then be achieved using a constant, relatively high concentration of a single metal precursor in the reaction zone.

[0042] Furthermore, it has been found that minimal etching is produced in the practice of this invention. See, for example... Figure 4 When the nucleation layer is deposited at a low concentration, substrate etching is negligible and the film is deposited with a smooth surface morphology. Once the nucleation layer is continuous and the substrate is not exposed to etching, the concentration of precursor vapor can be increased. Increasing the concentration of precursor vapor can improve the deposition rate and improve the step coverage.

[0043] In the method of the present invention, the precursor compound may be reacted with the surface or substrate of the desired microelectronic device in any suitable manner, such as in a single-wafer chamber, in a multi-wafer chamber, or in a furnace containing multiple wafers.

[0044] As used herein, the term "reducing gas" means a gas selected from hydrogen (H2), diborane (B2H6), silane (SiH4), and disilane (Si2H6). In certain cases, nitrogen-containing reducing gases, such as ammonia (NH3) and hydrazine (N2H4); C1-C4 alkyl hydrazines, such as methylhydrazine, tributylhydrazine, 1,1-dimethylhydrazine, and 1,2-dimethylhydrazine, may be suitable, but under some conditions will produce Mo or W nitride films instead of pure metal films. Similarly, in certain cases, carbon-containing reducing gases, such as alkanes, alkenes, and alkynes, may be suitable, but under some conditions will produce Mo or W nitride films instead of pure metal films. In one embodiment, the reducing gas is hydrogen.

[0045] The methods disclosed herein may include one or more purge gases as an optional step between the metal precursor and the reducing gas, and a carrier gas. The purge gas or carrier gas, used to purge unconsumed reactants and / or reaction byproducts, or as a diluent and carrier for the metal precursor and reducing gas, is an inert gas that does not react with the precursor. Exemplary gases include, but are not limited to, argon, nitrogen, helium, neon, and mixtures thereof. In some embodiments, a purge gas, such as Ar, is supplied to the reactor at a flow rate of about 10 sccm to about 10000 sccm over about 0.1 to 1000 seconds to purge unreacted material and any byproducts that may remain in the reactor. Furthermore, such inert gases can be used as carrier gases to vary the concentration of molybdenum or tungsten precursors and / or reducing gases as used herein.

[0046] As used herein, the term "microelectronic device" refers to semiconductor substrates used in the fabrication of microelectronic, integrated circuit, or computer chip applications, including 3D NAND structures, logic devices, DRAM, power devices, flat panel displays, and microelectromechanical systems (MEMS). It should be understood that the term "microelectronic device" is not intended to be limiting in any way and includes any substrate comprising n-type channel metal-oxide semiconductor (nMOS) and / or p-type channel metal-oxide semiconductor (pMOS) transistors that will ultimately become a microelectronic device or microelectronic assembly. Furthermore, the underlying substrate is not necessarily silicon, but may be an insulator such as glass or sapphire, a high-bandgap semiconductor such as SiC or GaN, or other materials suitable for fabricating circuits. Such microelectronic devices contain at least one substrate, which may be selected from, for example, silicon, SiO2, Si3N4, OSG, FSG, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boron nitride, antireflective coating, photoresist, germanium, germanium-containing, boron-containing, Ga / As, flexible substrate, porous inorganic material, metals such as copper and aluminum, and diffusion mask layers, such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. The film is compatible with a variety of subsequent processing steps, such as chemical mechanical planarization (CMP) and anisotropic etching processes.

[0047] Example

[0048] In the following examples, the thickness values ​​refer to the mass-equivalent thickness measured by X-ray fluorescence. The measurement technique measures the number of Mo atoms per unit area on the substrate with high precision. The theoretical density of Mo metal is approximately 10.28 g / cm³. 3This measurement is used to convert the film thickness to a mass-equivalent thickness using a model with uniform film thickness. It should be understood that poorly nucleated and highly rough films may be much thicker in some areas and even have no thickness in some areas (bare substrate).

[0049] Example 1

[0050] Chemical vapor deposition (CVD) was performed on a TiN substrate at 450°C, along with MoO2Cl2. The ampoule temperature was 40°C, the carrier gas flow rate was 25 sccm, and the H2 flow rate was 500 sccm, resulting in a concentration of 70 ppm at 80 Torr pressure. After 24 minutes, almost no Mo was deposited. (Metal equivalent thickness), and the resistivity of thin Mo films cannot be measured. See also Figure 1 .

[0051] Example 2

[0052] Chemical vapor deposition (CVD) was performed on a TiN substrate at 400°C, along with MoO2Cl2. The ampoule temperature was 60°C, the carrier gas flow rate was 50 sccm, and the H2 flow rate was 4000 sccm, resulting in a concentration of 20 ppm at 80 Torr pressure. After 10 minutes, discontinuous layers with separated nucleation sites were generated and deposited. The membrane is unmeasurable in terms of resistivity. See also Figure 2 .

[0053] Example 3

[0054] Pulsed chemical vapor deposition (PCVD) was performed on a TiN substrate at 390°C, along with MoO2Cl2. The ampoule temperature was 40°C, the carrier gas flow rate was 20 sccm, and the H2 flow rate was 1000 sccm, resulting in a concentration of 22 ppm at 80 Torr pressure. After 20 cycles, a smooth surface with a resistivity of 222 μΩ-cm was produced. Mo film. See also Figure 3 This example demonstrates that pulsed CVD schemes typically result in lower concentrations due to the pulse duration "on" and "off" and dilution over time. Therefore, the concentration achieved at the surface is not necessarily the same as the concentration retained on the surface and reacting with the reducing gas over time. Consequently, pulsed CVD schemes exhibit lower effective precursor concentrations at the surface over time compared to (continuous) CVD schemes.

[0055] Example 4

[0056] Pulsed chemical vapor deposition (PCVD) was used with MoO2Cl2 at a SiN substrate temperature of 400°C. The ampoule temperature was 40°C, the carrier gas flow rate was 20 sccm, and the H2 flow rate was 1000 sccm, resulting in a concentration of 22 ppm at 80 Torr pressure. After 200 cycles, a concentration of 22 ppm was achieved on the through-hole structure. Film. A good Mo film with an AFM RMS roughness of 0.684 nm was produced. See also Figure 4 .

[0057] Example 5

[0058] Chemical vapor deposition (CVD) was used with MoO2Cl2 at a PVD Mo substrate temperature of 390°C. The ampoule temperature was 40°C, the carrier gas flow rate was 20 sccm, and the H2 flow rate was 1000 sccm, resulting in a concentration of 30 ppm at 80 Torr pressure. After 20 minutes, [the ampoule was then...]. Mo film added to On a PVD Mo substrate. The resistivity of the CVD Mo film is 17 μΩ-cm. The well-formed Mo film produced at a substrate temperature of 390 °C demonstrates the high deposition rate of CVD Mo on PVD Mo. See also Figure 5 .

[0059] Example 6

[0060] Chemical vapor deposition (CVD) was performed on a TiN substrate at 450°C, along with MoO2Cl2. The ampoule temperature was 40°C, the carrier gas flow rate was 25 sccm, and the H2 flow rate was 1000 sccm, resulting in a concentration of 37 ppm at 80 Torr pressure. After 20 minutes, a substrate with a resistivity of 34.4 μΩ-cm was deposited. Film. When the bulk concentration is reduced by a factor of 2 compared to Example 1, a rough CVD Mo film can be deposited on TiN at a substrate temperature of 450°C. See also Figure 6 .

[0061] Example 7

[0062] A two-step chemical vapor deposition (CVD) method was used on a TiN-Mo substrate at a temperature of 390°C, along with MoO2Cl2. The ampoule temperature was 40°C, the carrier gas flow rate was 20 sccm, the H2 concentration was 1000 sccm, and the pressure was 80 Torr. In one experiment, the first step involved 45 cycles of pulsed CVD nucleation at a concentration of 22 ppm to deposit [the desired substance] on the TiN substrate. A thick Mo layer was formed. In the second experiment, the first step involved performing 45 cycles under the conditions described above. Immediately following this, the second step employed CVD under the same conditions as the first step, except for a higher concentration of 30 ppm. After 20 minutes, the total Mo film thickness was [missing information]. And ρ = 17.7 μΩ-cm. A good Mo film was produced on the TiN substrate, with resistivity and roughness comparable to the CVD Mo film deposited directly on the PVD Mo substrate. This resistivity is half that of the Mo film deposited in Example 6 without a low-concentration nucleation layer. See also Figure 7 (Regarding "Part B").

[0063] Pulsed CVD nucleation was used at 20 sccm and 10 min for CVD bulk deposition of (Mo) and T. sub =390℃ (substrate temperature); and H2 = 1000 sccm, the following comparative examples are produced.

[0064]

[0065] 1 XRD material composition

[0066] As can be seen from this data, the nucleation period of the deposition is approximately... and The deposition rate stops between intervals and is approximately equal to the settling rate. Increase to

[0067] The table below provides AFM roughness data, comparing Mo nucleation layers of different thicknesses, Mo deposition without nucleation layers, and extremely thick nucleation layers. Variations in nucleation layer thickness have minimal impact on the final Mo film roughness but a significant impact on the bulk Mo deposition rate.

[0068]

[0069] 1 Mo thickness

[0070] 2 Mo CVD deposition rate

[0071] 3 XRD material composition

[0072] 4 AFM RMS roughness (nm)

[0073] aspect

[0074] In a first aspect, a method for vapor-phase deposition of a molybdenum or tungsten film onto a surface comprises introducing a first precursor and a reducing gas into a reaction zone containing the surface until approximately [a certain value is achieved]. to approximately A film of a certain thickness has been deposited on the surface; a second precursor and a reducing gas are introduced into the reaction zone until a film of the desired thickness is deposited, wherein the concentration of the first precursor in the reaction zone is about 1% to about 75% of the concentration of the second precursor and wherein the first and second precursors may be the same precursor or different precursors.

[0075] In a second aspect, the present invention provides a method of the first aspect, wherein the concentration of the first precursor is about 10% to about 50% of the concentration of the second precursor.

[0076] In a third aspect, the present invention provides a method of the first or second aspect, wherein the surface is selected from nitrides, oxides, metals, semiconductors, and superconductors.

[0077] In a fourth aspect, the present invention provides a method for vapor-phase deposition of a molybdenum- or tungsten-containing film onto a surface of a microelectronic device in a reaction zone, said reaction zone being operated at a pressure of about 1 Torr to about 1000 Torr and a temperature of about 300°C to about 1000°C; wherein said surface is selected from nitrides, oxides, metals, semiconductors, and superconductors, and the method comprises:

[0078] a. A molybdenum or tungsten precursor is repeatedly introduced in pulses into a reaction zone containing a surface for a duration of approximately 0.1 seconds to approximately 120 seconds, followed by a pause of approximately 1 second to approximately 120 seconds, wherein the initial concentration of the precursor in the reaction zone is approximately 1 ppm to approximately 5000 ppm at its peak, while a reducing gas is continuously introduced into the reaction zone until a surface has been deposited with approximately to approximately Thickness of the film, and

[0079] b. A molybdenum or tungsten precursor is repeatedly introduced in a pulsed manner into the surface-containing reaction zone for a duration of about 0.1 seconds to about 120 seconds to reach a second precursor concentration, followed by a pause of about 1 second to about 120 seconds; wherein the second concentration of the precursor in the reaction zone is about 1.3 times to about 100 times the first precursor concentration, while a reducing gas is continuously introduced into the reaction zone until a film of the desired thickness has been deposited.

[0080] In a fifth aspect, the present invention provides a method of the fourth aspect, wherein the precursor is selected from WCl6, WCl5, WOCl4, MoO2Cl2, MoCl5, and MoOCl4.

[0081] In a sixth aspect, the present invention provides a method of the fourth or fifth aspect, wherein the precursor is MoO2Cl2.

[0082] In a seventh aspect, the present invention provides a method of the fourth, fifth, or sixth aspect, wherein the pressure in the reaction zone is about 20 Torr to about 200 Torr.

[0083] In an eighth aspect, the present invention provides a method of any one of the fourth to seventh aspects, wherein the first concentration of the precursor is about 20 ppm to about 500 ppm.

[0084] In a ninth aspect, the present invention provides a method of any one of the fourth to eighth aspects, wherein the temperature in the reaction zone is about 350°C to 500°C.

[0085] In a tenth aspect, the present invention provides a method for vapor-phase deposition of a molybdenum- or tungsten-containing film onto a surface of a microelectronic device in a reaction zone, said reaction zone being operated at a pressure of about 1 Torr to about 1000 Torr and a temperature of about 300°C to about 1000°C; wherein said surface is selected from nitrides, oxides, metals, semiconductors, and superconductors, and the method comprises:

[0086] a. A molybdenum or tungsten precursor is continuously introduced into a reaction zone containing a surface, wherein the initial concentration of the precursor in the reaction zone is from about 1 ppm to about 5000 ppm at its peak, while a reducing gas is continuously introduced into the reaction zone until a surface has been deposited with approximately to approximately Thickness of the film, and

[0087] b. A molybdenum or tungsten precursor is continuously introduced into a reaction zone containing a surface to achieve a second precursor concentration, wherein the second concentration of the precursor in the reaction zone is about 1.3 to about 100 times the first precursor concentration, while a reducing gas is continuously introduced into the reaction zone until a film of the desired thickness has been deposited.

[0088] In an eleventh aspect, the present invention provides a method of a tenth aspect, wherein the precursor is selected from WCl6, WCl5, WOCl4, MoO2Cl2, MoCl5, and MoOCl4.

[0089] In a twelfth aspect, the present invention provides a method of the tenth or eleventh aspect, wherein the precursor is MoO2Cl2.

[0090] In a thirteenth aspect, the present invention provides a method of any one of the tenth to twelfth aspects, wherein the pressure in the reaction zone is about 20 Torr to about 200 Torr.

[0091] In a fourteenth aspect, the present invention provides a method of any one of the tenth to thirteenth aspects, wherein the first concentration of the precursor is about 20 ppm to about 500 ppm.

[0092] In a fifteenth aspect, the present invention provides a method of any one of the tenth to fourteenth aspects, wherein the temperature in the reaction zone is about 350°C to 500°C.

[0093] In a sixteenth aspect, the present invention provides a method for vapor-phase deposition of a molybdenum- or tungsten-containing film onto a surface of a microelectronic device in a reaction zone operated at a pressure of about 1 Torr to about 1000 Torr and a temperature of about 300°C to about 1000°C; wherein the surface is selected from nitrides, oxides, metals, semiconductors, and superconductors, and the method comprises:

[0094] a. A molybdenum or tungsten precursor is repeatedly introduced into the surface-containing reaction zone for a first pulse duration of about 0.1 seconds to about 120 seconds, thereby achieving a first concentration of the precursor in the reaction zone, wherein the first concentration of the precursor in the reaction zone is about 1 ppm to about 5,000 ppm, and the reaction zone is flushed with an inert gas for about 1 second to about 120 seconds. A reducing gas is introduced into the reaction zone for a second pulse duration of about 0.1 seconds to about 120 seconds, and flushed with an inert gas for a duration of about 1 second to about 120 seconds, until a surface concentration of about [missing value] has been deposited. to approximately Thickness of the film, and

[0095] b. During a first pulse duration of about 0.1 seconds to about 120 seconds, a molybdenum or tungsten precursor is repeatedly introduced into the surface-containing reaction zone, thereby achieving a second precursor concentration in the reaction zone, wherein the second concentration of the precursor in the reaction zone is about 1.3 times to about 100 times the first concentration, and the reaction zone is flushed with an inert gas for about 1 second to about 120 seconds, and a reducing gas is introduced into the reaction zone during a second pulse duration of about 0.1 seconds to about 120 seconds, and flushed with an inert gas for a duration of about 1 second to about 120 seconds, until a film of the desired thickness has been deposited.

[0096] In a seventeenth aspect, the present invention provides a method of the sixteenth aspect, wherein the precursor is selected from WCl6, WCl5, WOCl4, MoO2Cl2, MoCl5, and MoOCl4.

[0097] In an eighteenth aspect, the present invention provides a method of the sixteenth or seventeenth aspect, wherein the precursor is MoO2Cl2.

[0098] In a nineteenth aspect, the present invention provides a method of any one of the sixteenth to eighteenth aspects, wherein the pressure in the reaction zone is about 20 Torr to about 200 Torr.

[0099] In a twentieth aspect, the present invention provides a method of any one of the sixteenth to nineteenth aspects, wherein the first concentration of the precursor is about 20 ppm to about 500 ppm.

[0100] In a twentieth aspect, the present invention provides a method in the twentieth aspect, wherein the temperature in the reaction zone is about 350°C to 500°C.

[0101] Therefore, based on the described illustrative embodiments of the invention, those skilled in the art will readily understand that other embodiments can be made and used within the scope of the appended claims. Numerous advantages of the invention covered in this document have been set forth in the foregoing description. However, it should be understood that the invention is illustrative in many respects only. The scope of the invention is, of course, defined by the language of the appended claims.

Claims

1. A method for vapor-phase deposition of a molybdenum or tungsten film onto a surface of a microelectronic device in a reaction zone, said reaction zone being operated at a pressure of 1 Torr to 1000 Torr and a temperature of 300°C to 500°C; wherein said surface is selected from nitrides, oxides, and metals, the method comprising: a. A molybdenum or tungsten precursor is repeatedly introduced in pulses into the reaction zone containing the surface, each pulse lasting 0.1 to 120 seconds followed by a pause of 1 to 120 seconds, wherein the concentration of the first precursor in the reaction zone is 1 ppm to 5000 ppm at its peak, while a reducing gas is continuously introduced into the reaction zone until a film with a thickness of 3 Å to 25 Å has been deposited. b. A molybdenum or tungsten precursor is repeatedly introduced in pulses into the reaction zone containing the surface, each pulse lasting from 0.1 seconds to 120 seconds, thereby reaching a second precursor concentration, followed by a pause of 1 second to 120 seconds; wherein the second precursor concentration in the reaction zone is 1.3 to 100 times the first precursor concentration, while a reducing gas is continuously introduced into the reaction zone until a film of the desired thickness has been deposited. The precursors are selected from WCl6, WCl5, WOCl4, MoO2Cl2, MoCl5, and MoOCl4.

2. The method according to claim 1, wherein the precursor is MoO2Cl2.

3. The method according to claim 1, wherein the pressure in the reaction zone is 20 Torr to 200 Torr.

4. The method of claim 1, wherein the concentration of the first precursor of the precursor is from 20 ppm to 500 ppm.

5. The method according to claim 1, wherein the temperature in the reaction zone is 350°C to 500°C.

6. A method for vapor-phase deposition of a molybdenum or tungsten film onto a surface of a microelectronic device in a reaction zone, said reaction zone being operated at a pressure of 1 Torr to 1000 Torr and a temperature of 300°C to 500°C; wherein said surface is selected from nitrides, oxides, and metals, the method comprising: a. A molybdenum or tungsten precursor is continuously introduced into a reaction zone containing the surface, wherein the concentration of the first precursor in the reaction zone is 1 ppm to 5000 ppm at its peak, while a reducing gas is continuously introduced into the reaction zone until a film with a thickness of 3 Å to 25 Å has been deposited. b. A molybdenum or tungsten precursor is continuously introduced into the reaction zone containing the surface to achieve a second precursor concentration, wherein the second precursor concentration in the reaction zone is 1.3 to 100 times the first precursor concentration, while a reducing gas is continuously introduced into the reaction zone until a film of the desired thickness has been deposited. The precursors are selected from WCl6, WCl5, WOCl4, MoO2Cl2, MoCl5, and MoOCl4.

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