JP2019044266A - Layer formation method - Google Patents

Abstract

To provide an improved method for forming a sedimentary layer having improved quality on a substrate.SOLUTION: A formation method of a layer includes steps of: depositing a seed layer on a substrate; and depositing a bulk layer on the seed layer. In the method, deposition of the seed layer includes steps of: supplying a first precursor containing a metal and a halogen atom to the substrate; and supplying a first reaction material to the substrate, and deposition of the bulk layer includes steps of: supplying a second precursor containing a metal and a halogen atom to the seed layer; and supplying a second reaction material to the seed layer.SELECTED DRAWING: Figure 1

Description

Related application

(Cross-reference to related applications)
[0001] This application is a continuation-in-part of US Non-Provisional Application No. 15 / 691,241 (filed on August 30, 2017) entitled "Layer Forming Method", and the United States entitled "Layer Forming Method". This application claims the benefit of Provisional Patent Application No. 62 / 607,070, filed December 18, 2017, both applications incorporated herein by reference.

  FIELD [0002] The present disclosure relates generally to methods of forming a layer on a substrate. More specifically, the present disclosure sequentially repeats an atomic layer deposition (ALD) cycle or a chemical vapor deposition (CVD) process to form at least a layer on a substrate having a gap generated during manufacture of a feature. For forming part. The layers on the substrate can be used for the production of semiconductor devices.

  [0003] In atomic layer deposition (ALD) and chemical vapor deposition (CVD), a substrate is a first precursor and a first reactant suitable to react to become a desired layer on the substrate. Exposed. A layer may be deposited in the gaps created during the manufacture of the features on the substrate to fill the gaps.

  [0004] In ALD, a substrate is exposed to a pulse of a first precursor, and a monolayer of the first precursor may be chemisorbed on the surface of the substrate. The surface site may be occupied by the whole of the first precursor or a fragment thereof. The reaction may be chemically self-limiting, as the first precursor does not adsorb or react with the portion of the first precursor already adsorbed to the substrate surface. The excess first precursor is then purged, for example, by the supply of inert gas and / or the removal of the first precursor from the reaction chamber. The substrate is then exposed to a pulse of the first reactant, which chemically reacts with all or a portion of the adsorbed first precursor until the reaction is complete, and the surface is a monolayer of reaction product Covered with

  It has been recognized that there may be a need to improve the quality of deposited layers.

  [0006] An improved method of forming a deposited layer on a substrate may be needed. Thus, there is provided a method of forming a layer comprising the steps of providing a substrate with a gap created during manufacture of the features, depositing a seed layer on the substrate, and depositing a bulk layer on the seed layer. It can be provided. The deposition of the seed layer can include the steps of providing a first precursor comprising a metal and a halogen atom to the substrate, and providing a first reactant to the substrate, wherein the first step A portion of the precursor and the first reactant react to form at least a portion of the seed layer. The deposition of the bulk layer can include the steps of providing a second precursor comprising a metal and a halogen atom to the seed layer, and providing a second reactant to the seed layer, wherein A portion of the precursor and a second reactant react to form at least a portion of the bulk layer on the seed layer. The first and second precursors may be different.

  [0007] Having different first and second precursors for the seed and bulk layers allows the properties of the seed and bulk layers to be optimized such that the quality of all layers is improved. . The first and second reactants may be the same and may include hydrogen atoms.

  [0008] In some other embodiments, a method of processing a semiconductor is provided. The method comprises the steps of depositing a metal layer in the interstices of the substrate, thereby filling the interstices.

[0009] These and other features, aspects, and advantages of the invention disclosed herein are described below and are intended to be illustrative with reference to the drawings of some embodiments, It does not limit the present invention.
[00010] Figures la and lb show a flow chart outlining a method of depositing a layer according to one embodiment. [00011] FIG. 2 shows a cross-sectional view of a gap structure on a layer-filled substrate, according to one embodiment.

  [00012] A metal layer may be required as a conductive layer of a semiconductor device. The gaps created during the fabrication of integrated circuit device features may be filled with a metal layer. The gaps can have a high aspect ratio such that their depth is much larger than the width.

  [00013] The gap may extend vertically into an already manufactured layer with a substantially horizontal upper surface. A vertical, metal-filled gap can be used, for example, for a word line of a dynamic random access memory (DRAM) type memory integrated circuit. Vertically filled, metal-filled gaps can also be used, for example, in logic integrated circuits. For example, the metal filled gap can be used as a gate fill for P-type metal oxide semiconductor (PMOS) or complementary metal oxide semiconductor (CMOS) integrated circuits or source / drain trench contacts.

  [00014] The gaps may be arranged horizontally in the layers already produced. Again, the gaps can have a high aspect ratio such that their depth in the horizontal direction is much greater than the width here. A horizontal, metal-filled gap can be used, for example, for the word lines of 3D NAND type memory integrated circuits. The gaps may be arranged in a combination of vertical and horizontal directions.

  [00015] The surface of the interstices may comprise a type of deposition material. Alternatively, the surface of the gap may comprise different types of deposition material. The surface of the gap may, for example, comprise aluminum oxide and / or titanium nitride. For example, when a molybdenum conductive layer may be required in the gap, it may be difficult to deposit molybdenum on different gap materials. It may be necessary to cover the entire surface of the gap with a molybdenum layer to fill the complete gap. In addition, a molybdenum layer may cover the entire surface of the gap, including different types of materials.

  [00016] To fill the complete gap, a seed layer may be deposited in the gap and a bulk layer may be deposited on the seed layer. The seed layer can be formed by sequentially repeating pretreatment atomic layer deposition (ALD). Alternatively, the seed layer may be formed by a chemical vapor deposition (CVD) process. The CVD process may be pulsed, where the first precursor is pulsed onto the substrate while the first reactant is continuously fed to the substrate or vice versa May be. The bulk layer can be deposited on the seed layer by sequentially repeating the bulk ALD cycle. Alternatively, the bulk layer may be deposited on the seed layer by a CVD process. The CVD process may be pulsed, where the second precursor is pulsed onto the substrate while the second reactant is continuously fed to the substrate or vice versa .

  [00017] Figures 1a and 1b show a flow chart outlining a method of layer deposition according to an embodiment where a seed layer can be deposited in the gap and a bulk layer can be deposited on the seed layer. Pretreatment ALD cycle 1 for the seed layer may be shown in FIG. 1a and bulk ALD cycle 2 for the bulk layer may be shown in FIG. 1b.

  [00018] Providing a substrate with a gap in step 3 into the reaction chamber, then providing a first precursor comprising metal and halogen atoms in step 5 to the substrate during a first feed period T1. (See Figure 1a). Thereafter, additional supply of the first precursor to the substrate, for example by removing (eg, purging) a portion of the first precursor from the reaction chamber, eg, during the first removal period R1 of step 7. Can stop. Further, the cycle may include the step 9 of supplying the first reactant to the substrate during the second supply period T2. The first precursor and a portion of the first reactant may react to form at least a portion of the seed layer on the substrate. Usually, a few (approximately 50) cycles may be required before the deposition of the seed layer begins. For example, during the second removal period R1 of step 11, the additional supply of the first reactant to the substrate is stopped by removing (eg, purging) a portion of the first reactant from the reaction chamber can do.

  [00019] The first precursor and the first reactant may be selected to have proper nucleation on the surface of the gap. The pretreatment ALD cycle 1 can be repeated N times to deposit the seed layer, where N is selected between 100-1000, preferably 200-800, more preferably 300-600. The seed layer can have a thickness of 1 to 20 nm, preferably 2 to 10 nm, more preferably 3 to 7 nm.

  [00020] After pretreatment, ALD cycle 1 is repeated N times. During the third delivery period T3 of the bulk ALD cycle 2, a first precursor comprising metal and halogen atoms can be provided to the substrate in step 11 (see FIG. 1b). This may be performed in the same reaction chamber as pretreatment ALD cycle 1 of FIG. 1a or in a different reaction chamber. When the temperature requirements for the pretreatment cycle are different, it may be advantageous to perform the bulk ALD cycle in a different reaction chamber than the pretreatment ALD cycle. Thus, substrate transport may be required. Thereafter, additional supply of the second precursor to the substrate, for example by removing (eg, purging) a portion of the second precursor from the reaction chamber, eg, during the third removal period R3 of step 13. Can stop.

  [00021] Further, the cycle may include the step 15 of delivering a second reactant to the substrate during a fourth delivery period T4. The second precursor and a portion of the second reactant may react to form at least a portion of the bulk layer on the substrate. For example, during the fourth removal period R4 of step 17, the additional supply of the second reactant to the substrate is stopped by removing (eg, purging) a portion of the second reactant from the reaction chamber can do. The second precursor and the second reactant may be selected to have appropriate electronic properties. For example, it can be selected to have a low electrical resistivity. The molybdenum film is less than 3000 μΩ-cm, or less than 1000 μΩ-cm, or less than 500 μΩ-cm, or less than 200 μΩ-cm, or less than 100 μΩ-cm, or less than 50 μΩ-cm, or less than 25 μΩ-cm, or 15 μΩ-cm or In addition, it can have an electrical resistivity of less than 10 μΩ-cm.

  [00022] Bulk ALD cycle 2 for the bulk layer can be repeated M times, where M is selected between 200 and 2000, preferably 400 to 1200, more preferably 600 to 1000. The bulk layer can have a thickness of 1 to 100 nm, preferably 5 to 50 nm, more preferably 10 to 30 nm.

  [00023] The first and second precursors may comprise the same metal atom. The metal may be a transition metal atom. The transition metal atom may be molybdenum.

[00024] The first and second precursors may comprise the same halogen atom. The halogen atom may be chloride. Having the same halogen atoms can simplify the qualification conditions of fabrication tools and processes, as only one halogen needs to be evaluated. The first precursor may comprise molybdenum pentachloride (MoCl ₅ ).

  [00025] The process temperature of the reaction chamber may be selected as 300-800 0 C, preferably 400-700 0 C, more preferably 450-550 0 C during the pretreatment ALD cycle. The vessel in which the first precursor evaporates may be maintained at 40 to 100 ° C., preferably 60 to 80 ° C., more preferably around 70 ° C.

[00026] The second precursor may comprise additional atoms that are not metals or halogen atoms. The additional atom may be a chalcogen. The chalcogen may be oxygen, sulfur, selenium or tellurium. The second precursor may comprise molybdenum dichloride dioxide (VI) (MoO ₂ Cl ₂ ).

  [00027] The process temperature of the reaction chamber may be 300-800 ° C, preferably 400-700 ° C, more preferably 500-650 ° C during the bulk ALD cycle. The vessel in which the second precursor evaporates may be maintained at 20-150 ° C., preferably 30-120 ° C., more preferably 40-110 ° C.

  [00028] The step of supplying the first and / or second precursor to the reaction chamber is selected from 0.1 to 10 seconds, preferably 0.5 to 5 seconds, more preferably 0.8 to 2 seconds May take up to T1 and T3. For example, T1 may be 1 second and T3 may be 1.3 seconds. The flow rate of the first or second precursor to the reaction chamber may be selected from 50 to 1000 sccm, preferably 100 to 500 sccm, more preferably 200 to 400 sccm. The pressure of the reaction chamber may be selected from 0.1 to 100 Torr, preferably 1 to 50 Torr, more preferably 4 to 20 Torr.

[00029] One or both of the first and second reactants can have a halogen atom. At least one of the first and second reactants may comprise hydrogen (H ₂ ). The first and second reactants may be the same. The step of supplying the first and / or second reactants to the reaction chamber for duration T2, T4 takes from 0.5 to 50 seconds, preferably from 1 to 10 seconds, more preferably from 2 to 8 seconds There is. The flow rate of the first or second reactant to the reaction chamber may be selected from 50 to 50000 sccm, preferably 100 to 20000 sccm, more preferably 500 to 10000 sccm.

[00030] Silanes can be considered for the first and / or second reactants. The general formula of the silane is Si _x H 2 _{(x + 2)} , where x is an integer 1, 2, 3, 4. Silane (SiH ₄ ), disilane (Si ₂ H ₆ ) or trisilane (Si ₃ H ₈ ) may be suitable examples of the first and / or second reactant having a hydrogen atom.

  [00031] Remove a portion of at least one of the first precursor, the first reactant, the second precursor and the second reactant from the reaction chamber for a duration R1, R2, R3 or R4 For example, the step of purging can be performed for 0.5 to 50 seconds, preferably 1 to 10 seconds, more preferably 2 to 8 seconds. After supplying the first precursor to the substrate, after supplying the first reactant to the substrate, after supplying the second precursor to the seed layer, and supplying the second reactant to the seed layer And then using at least one of the first precursor, the first reactant, the second precursor and the second reactant for a duration R1, R2, R3 or R4 using a purge. It can be removed from the reaction chamber. The removal can be achieved by pumping and / or supplying a purge gas. The purge gas may be an inert gas such as nitrogen.

  [00032] The method can be used for single or batch wafer ALD equipment. The method comprises the steps of providing a substrate to a reaction chamber, wherein a pre-treatment ALD cycle in the reaction chamber comprises the steps of: supplying a first precursor to the substrate in the reaction chamber; reacting a portion of the first precursor Purging from the chamber, supplying the first reactant to the substrate in the reaction chamber, and purging a portion of the first reactant from the reaction chamber may be included. The method further includes the step of providing a substrate to the reaction chamber, wherein the bulk ALD cycle in the reaction chamber comprises the step of providing a second precursor to the substrate in the reaction chamber, reacting a portion of the second precursor Purging from the chamber, supplying a second reactant to the substrate in the reaction chamber, and purging a portion of the second reactant from the reaction chamber.

  [00033] Exemplary single-wafer reactors specifically designed to perform ALD processes are: ASM International NV (Almere, The Netherlands) from Pulsar (R), Emerald (R), Dragon (R) and It is marketed under the trade name Eagle®. The method can also be practiced with batch wafer reactors (eg, vertical furnaces). For example, the deposition process is described in ASM International N. V. Can also be implemented with the A412.TM. vertical furnace, which is commercially available from The furnace may have 150 semiconductor substrates with a diameter of 300 mm, or a process chamber that can accommodate an amount of wafers.

  [00034] The wafer reactor can have a controller and a memory that can control the reactor. In accordance with embodiments of the present disclosure, the memory can be programmed with a program to supply precursors and reactants to the reaction chamber when executed by the controller.

  [00035] FIG. 2 shows a cross-sectional view of a gap structure on a layer-filled substrate, according to one embodiment of the present disclosure. As shown herein, the gap can extend vertically and horizontally into an already manufactured layer with a substantially horizontal upper surface.

  [00036] The gap can have a high aspect ratio such that the vertical and / or horizontal depth is much larger than the width. For example, in the vertical direction, the gap has a width of 207 nm at the top, 169 nm at the middle and 149 nm at the bottom, while the depth of the gap is much larger at 432 nm. For example, in the horizontal direction, the first gap from the top has a width of 34 nm, while the gap depth is much larger at 163 nm (rounded off). The aspect ratio of the gap (gap depth / gap width) can be more than about 2, more than about 5, more than about 10, more than about 20, more than about 50, more than about 75 In the case of parts, it can be more than about 100, or more than about 150, or even more than about 200.

  [00037] It may be difficult to determine the aspect ratio to the gap, but in this context, the aspect ratio is the total surface area of the wafer or part of the wafer relative to the planar surface area of the wafer or part of the wafer It can be pointed out that the ratio can be replaced by the surface enhancement effect ratio. The surface enhancement effect ratio of the gap (gap surface / wafer surface) can be more than about 2, more than about 5, more than about 10, more than about 20, more than about 50, more than about 75, In some cases, more than about 100, or more than about 150, or even more than about 200.

[00038] The surface of the gap may comprise different types of deposition material 19,21. For example, the surface may comprise Al ₂ O ₃ or TiN.

  [00039] The conformal metal layer 23 deposits the seed layer by sequentially repeating the pretreatment ALD cycle with the first precursor and the bulk layer by sequentially repeating the bulk ALD cycle with the second precursor By depositing, it is deposited on the surface of the gap. Details of the method used are shown in FIGS. 1a and 1b and the associated description. In some embodiments, the deposited film comprising Mo has a step greater than about 50%, greater than about 80%, greater than about 90%, greater than about 95%, greater than about 98%, greater than about 99% It may have coverage.

[00040] The first and second precursors may comprise the same metal atom (eg, a transition metal atom such as molybdenum). The first and second precursors may comprise the same halogen atom (e.g. chloride). The first precursor may comprise MoCl5. The second precursor may comprise additional atoms that are not metals or halogen atoms (e.g. chalcogenide atoms such as oxygen). The second precursor may comprise molybdenum dichloride dioxide (VI) (MoO ₂ Cl ₂ ). The method may be carried out in an atomic layer deposition apparatus. For example, the deposition process may be performed on an EMERALD® XP ALD apparatus.

[00041] The first and second reactants is a hydrogen (H _2), which during the time duration of 5 seconds in the reaction chamber T2, T4, was supplied at a flow rate of 495Sccm. A nitrogen purge gas is supplied after the first precursor, after the first reactant, after the second precursor, and after the second reactant for a duration of 5 seconds R1, R2 , R3 or R4 was used.

  [00042] During the pretreatment and bulk ALD cycles, the process temperature was approximately 550 0 C and the pressure was approximately 10 Torr. The vessel in which the first precursor was evaporated was approximately 70 ° C. The vessel in which the second precursor was evaporated was approximately 35 ° C.

  [00043] A seed layer of about 4.6 nm was deposited using 500 cycles of pretreatment ALD cycle and a bulk layer of about 21.4 nm was deposited using 800 cycles of bulk ALD cycle. As shown, the molybdenum layer 23 was deposited very uniformly on the surface of the gap and had a total thickness of about 26 nm.

It is believed that the orientation of the gap (whether horizontal or vertical) and the width of the gap do not substantially affect the thickness of layer 23. Furthermore, it is believed that the material of the surface does not affect the thickness of layer 23, whether it is Al ₂ O ₃ 19 or TiN 21. In this way it is possible to make a gap filled with metal with good uniformity.

  [00045] The method can also be used for spatial atomic layer deposition equipment. In space ALD, precursors and reactants are continuously supplied to different physical sections, and the substrate moves between the sections. In the presence of a substrate, at least two sections can be provided in which a half reaction can occur. When a substrate is present in such a semi-reactive section, a monolayer can be formed from the first or second precursor. The substrate is then transferred to a second half reaction zone where the ALD cycle is completed with the first or second reactants to form one ALD monolayer. Alternatively, the position of the substrate may be fixed, the gas supply may be moved, or some combination of the two. This order may be repeated to obtain thicker films.

[00046] According to an embodiment of the spatial ALD apparatus, the method comprises
Placing the substrate in a reaction chamber comprising a plurality of sections, each section being separated by a gas curtain from an adjacent section;
Supplying a first precursor to the substrate of the first section of the reaction chamber;
Moving the substrate surface laterally to the reaction chamber through the gas curtain to the second section of the reaction chamber;
Supplying a first reactant to the substrate of the second section of the reaction chamber to form a seed layer;
Moving the substrate surface laterally relative to the reaction chamber through the gas curtain;
Repeating the supply of the first precursor and the reactant, including laterally moving the substrate surface relative to the reaction chamber, to form a seed layer.

[00047] In order to form the bulk layer, the method further comprises
Placing the substrate in a reaction chamber comprising a plurality of sections, each section being separated by a gas curtain from an adjacent section;
Supplying a second precursor to the substrate of the first section of the reaction chamber;
Moving the substrate surface laterally to the reaction chamber through the gas curtain to the second section of the reaction chamber;
Supplying a second reactant to the substrate of the second section of the reaction chamber to form a bulk layer;
Moving the substrate surface laterally relative to the reaction chamber through the gas curtain;
Repeating the supply of the second precursor and the reactant, including laterally moving the substrate surface relative to the reaction chamber, to form a bulk layer.

  [00048] The first and second precursors may be different. The first and second reactants may be the same and may include hydrogen atoms.

  [00049] According to one embodiment, the seed layer can be deposited by a chemical vapor deposition (CVD) process, wherein the first precursor and the first reactant are provided simultaneously to the substrate . The bulk layer can be deposited by a CVD process, and again the second precursor and the second reactant can be provided simultaneously to the substrate.

  [00050] The CVD process may be a pulsed CVD process, wherein the first precursor is supplied to the substrate in pulses while the reactant is supplied to the substrate continuously. It may be advantageous that higher concentrations of reactants may reduce the concentration of halogen. High concentrations of halogen can damage semiconductor devices on the substrate.

  [00051] For example, in a pulsed CVD process on the seed layer, the first precursor molybdenum pentachloride (MoCl5) may be provided in a 1 second pulse, alternating with a 5 second purge gas flow. The first reactant hydrogen may be supplied continuously at a flow rate of 500 sccm and the substrate may be maintained at 550 ° C.

  [00052] An exemplary single-wafer reactor specifically designed to perform the CVD process is commercially available from ASM International NV (Almere, The Netherlands) under the trade name Dragon®. The method can also be practiced with batch wafer reactors (eg, vertical furnaces). For example, the deposition process is described in ASM International N. V. It can also be carried out with the A400TM, or A412TM vertical furnace, which is commercially available from The furnace may have a process chamber that can accommodate 150 semiconductor substrates, or quantities of wafers.

  [00053] For the production of 3D NAND memories, the word lines can have gaps that require low resistivity metal fill. Existing solutions may utilize TiN as a seed layer for CVD tungsten gap filling. In current fluorine based tungsten deposition processes, fluorine from WF6 precursors can diffuse. A thick (= 3 nm) TiN barrier may be needed to avoid fluorine diffusion and attack of the high dielectric constant (high-k) Al 2 O 3 film by the diffused fluorine. However, the high resistivity of TiN films (800 μΩ-cm at 3 nm) results in an increase in TiN / W stack resistivity, which may not be desirable.

  [00054] There may be a need for improved methods of forming low resistivity, but fluorine free, deposited layers on substrates. Thus, a method of forming a layer, including providing a substrate with a gap created during manufacture of the features, depositing a seed layer on the substrate, and depositing a bulk layer on the seed layer Can be provided. Depositing the bulk layer can include depositing a bulk layer on top of the seed layer, supplying a second precursor comprising a transition metal such as tungsten.

[00055] The second precursor may comprise a halogen such as chloride to deposit the bulk layer. The second precursor may be tungsten pentachloride (V) (WCl ₅ ) or tungsten hexachloride (VI)) (WCl ₆ ). The bulk layer can be deposited by reacting tungsten (V) chloride (V) (WCl ₅ ) or tungsten hexachloride (VI) (WCl ₆ ) with hydrogen H ₂ in an ALD or CVD mode of operation. For example, the reaction of WCl ₅ can be accomplished at a temperature of 450 ° C. and a pressure of 40 Torr. The precursors can be provided in an ALD or CVD mode of operation.

[00056] The seed layer may be deposited with molybdenum containing a first precursor that reacts with hydrogen. The resistivity of the seed layer using molybdenum can be 107 μΩ-cm at 3 nm, which is lower than that of the TiN layer. Good gap filling was achieved using this approach, especially for a stack thickness of 15 nm (corresponding to gap filling of a 30 nm CD structure). Deposit the tungsten layer without using fluorine by using tungsten pentachloride (V) (WCl ₅ ) or tungsten hexachloride (VI) (WCl ₆ ) to deposit the bulk layer on the seed layer However, it is still possible to have low resistivity. The precursor of the seed layer may comprise a transition metal (e.g. molybdenum (Mo)), a halogen (e.g. chloride (Cl)) and optionally a chalcogenide (e.g. oxygen (O)). The precursor of the seed layer may be, for example, pentachloride (MoCl ₅ ) or molybdenum (VI) dichloride dichloride (MoO ₂ Cl ₂ ), both of which react with hydrogen. When molybdenum pentachloride (MoCl ₅ ) is used, the partial pressure of hydrogen may be 100 times lower than that of molybdenum (VI) dichloride dioxide (MoO ₂ Cl ₂ ).

  [00057] The deposition rate of the molybdenum seed layer may be 1.2 angstroms / cycle. For comparison, the deposition rate of the TiN seed layer may be 0.6 Å / cycle under the same conditions. Thus, the deposition rate of the molybdenum seed layer may be sufficient.

[00058] The metal deposited on the seed layer may be copper. The second precursor may comprise copper. The second precursor may comprise a halogen such as chloride to deposit the bulk layer. The second precursor may comprise copper (II) dichloride (CuCl ₂ ) or copper chloride (CuCl). The precursors can be provided in an ALD or CVD mode of reaction with hydrogen.

  [00059] The metal deposited on the seed layer is a transition from the group Ti, V, Cr, Mn, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir and Pt. It may be metal or noble metal. In some embodiments, the layer can include Co or Ni.

  [00060] In additional embodiments, the seed or bulk layer is about 40 at. Less than about 30 at. Less than about 20 at. Less than about 10 at. Less than about 5 at. Less than%, or even about 2 at. % Oxygen can be included. In further embodiments, the seed or bulk layer is about 30 at. Less than about 20 at. Less than about 10 at. Less than about 5 at. Less than%, or about 2 at. %, Or even about 1 at. It may contain less than% hydrogen. In some embodiments, the seed or bulk layer is about 10 at. %, Or about 5 at. Less than about 1 at. % Or less, or even about 0.5 at. % Or less of halide or chloride may be included. In still further embodiments, the seed or bulk layer is about 10 at. % Or less, or about 5 at. Less than%, or about 2 at. Less than%, or about 1 at. % Or less, or even about 0.5 at. It may contain less than% carbon. In the embodiments outlined herein, atomic percent (at.%) Concentrations of elements may be determined utilizing Rutherford backscattering (RBS).

  [00061] In some embodiments of the present disclosure, forming a semiconductor device structure, such as a semiconductor device structure, can include forming a gate electrode structure comprising a molybdenum film, the gate electrode structure comprising about 4 Have an effective work function of greater than .9 eV, or greater than about 5.0 eV, or greater than about 5.1 eV, or greater than about 5.2 eV, or greater than about 5.3 eV, or even greater than about 5.4 eV . In some embodiments, the effective work function values described above are for an electrode structure comprising a molybdenum film having a thickness of less than about 100 angstroms, or less than 50 angstroms, or less than about 40 angstroms, or even less than 30 angstroms. Can be shown.

  [00062] Those skilled in the art will appreciate that various omissions, additions, and modifications may be made to the processes and structures described above without departing from the scope of the present invention. It is contemplated that various combinations or subcombinations of particular features and aspects of the embodiments may be made and still be within the scope of the description. Various features and aspects of the disclosed embodiments can be combined or substituted with one another in order. All such modifications and variations are intended to be included within the scope of the present invention as defined by the appended claims.

Claims (28)

A method of forming a layer,
Providing a substrate with a gap created during manufacture of the feature;
Depositing a seed layer on the substrate;
Depositing a bulk layer on said seed layer,
The deposition of the seed layer is
Supplying a first precursor having a metal and a halogen atom to the substrate;
Supplying a first reactant to the substrate, wherein a portion of the first precursor and the first reactant react to form at least a portion of the seed layer,
The deposition of the bulk layer is
Supplying a second precursor having a metal and a halogen atom to the seed layer;
Supplying a second reactant to the seed layer, wherein a portion of the second precursor and the second reactant react to form at least a portion of the bulk layer on the seed layer. ,
The method wherein the first and second precursors may be different.   The method of claim 1, wherein at least one of the first and second reactants comprises a hydrogen atom. 3. The method of claim _2, wherein at least one of the first and second reactants comprises hydrogen (H2).   The method of claim 1, wherein the first and second precursors are the same metal atom.   The method of claim 1, wherein at least one of the first and second precursors comprises a transition metal atom.   6. The method of claim 5, wherein the transition metal atom is molybdenum.   The method of claim 1, wherein the first and second precursors comprise the same halogen atom.   The method according to claim 1, wherein the halogen atom is a chloride. The method of claim 1, wherein the first precursor comprises molybdenum pentachloride (MoCl ₅ ).   The method of claim 1, wherein the second precursor comprises an additional atom that is not a metal or a halogen atom.   11. The method of claim 10, wherein the additional atom is a chalcogenide.   The method according to claim 11, wherein the chalcogenide is oxygen. The method according to claim 12, wherein the second precursor comprises molybdenum dichloride dioxide (VI) (MoO ₂ Cl ₂ ).   The method according to claim 1, wherein at least one of the first and second precursors is pulsed to the reaction chamber, and the pulse is 0.1 to 10 seconds.   The method according to claim 1, wherein the flow rate of the first or second precursor to the reaction chamber is 50 to 1000 sccm.   The method of claim 1, wherein the flow rate of the first or second reactant to the reaction chamber is 50 to 50000 sccm.   The method of claim 1, wherein the pressure of the reaction chamber is 0.1 to 100 Torr.   The method according to claim 1, wherein the process temperature is 300 to 800C.   Repeating an atomic layer deposition (ALD) cycle wherein deposition of at least one of the seed and bulk layers comprises sequentially supplying the first or second precursor to the substrate, and the first or second And B. supplying the following reactants to the substrate.   The substrate is purged for 0.5 to 50 seconds between the supply of the first precursor, the first reactant, the second precursor, or the second reactant to the substrate. 20. The method of claim 19, wherein   20. The method of claim 19, wherein providing the first and / or second reactants to the reaction chamber takes 0.5 to 50 seconds.   The method according to claim 19, wherein the pretreatment ALD cycle is repeated 100 to 1000 times for deposition of the seed layer, and the bulk ALD cycle is repeated 200 to 2000 times for deposition of the bulk layer. .   The method according to claim 1, wherein the deposition of the at least one of the seed and bulk layers comprises a chemical vapor deposition (CVD) process, and the precursor is provided to the substrate simultaneously with the reactants.   The method according to claim 5, wherein the transition metal atom is tungsten (W).   The method of claim 1, wherein the second precursor comprises tungsten (W). 26. The method of claim 25, wherein the second precursor comprises tungsten pentachloride (V) (WCl ₅ ) or tungsten hexachloride (VI) (WCl ₆ ).   The method of claim 1, wherein the second precursor comprises copper. The second precursor comprises cupric chloride (II) (CuCl ₂₎ or copper chloride (CuCl), The method of claim 24.