# Patent

## Title
Method of growing electrical conductors

## Abstract

A method for forming a conductive thin film includes depositing a metal oxide thin film on a substrate by an atomic layer deposition (ALD) process. The method further includes at least partially reducing the metal oxide thin film by exposing the metal oxide thin film to a reducing agent, thereby forming a seed layer. In one arrangement, the reducing agent comprises one or more organic compounds that contain at least one functional group selected from the group consisting of —OH, —CHO, and —COOH. In another arrangement, the reducing agent comprises an electric current.

## Background
CLAIM OF PRIORITY
The present application is a continuation-in-part of U.S. patent application Ser. No. 10/300,169, filed Nov. 19, 2002 now U.S. Pat. No. 6,887,795 which is a continuation of U.S. patent application Ser. No. 09/858,820, filed May 15, 2001, issued Nov. 19, 2002 as U.S. Pat. No. 6,482,740 B2 which claims the benefit under 35 U.S.C. §119(a) of Finnish Patent Application No. 20001163, filed May 15, 2000, each of which are incorporated in their entireties by reference herein.


BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to the manufacturing of integrated circuits (ICs), and particularly to the seed layers in damascene and dual damascene processes, gate metals of thin film transistors and capacitor electrodes in ICs.
More particularly the present invention relates to a method of depositing seed layers for a damascene and dual damascene structures, gate metals of thin film transistors and capacitor electrodes in ICs by an atomic layer deposition (ALD) method.
2. Description of the Related Art
The atomic layer deposition (ALD) method of depositing thin films has several attractive features including excellent step coverage, even on large areas, and a dense and pinhole-free structure. Therefore, it is of great interest to apply ALD to the deposition of metallization layers of advanced integrated circuits (ICs), where the continuously increasing packing density and aspect ratio set higher and higher demands upon the metallization layers. Applications where high quality metallization is particularly needed are dual damascene structures, gates in transistors and capacitors in ICs. However, due to the fact that ALD is based on sequential self-saturating surface reactions of source chemical compounds, depositing high quality elemental metal thin films by ALD is very difficult.
In ALD, the source chemical molecules chemisorb on the substrate via active sites on the substrate surface. Typical active sites for metal source chemicals are —OH, —NH2 and —NH groups. Metal-oxygen-metal bridges on the surface may also act as active sites. When a metal source chemical molecule reacts with the active site, a strong bond is formed between the surface and the ligand of the source chemical molecule is simultaneously released as a by-product.
In ALD, films grow with a constant growth rate. Each deposition cycle produces one molecular layer of the deposited material on the substrate surface. Usually the growth rate is well below one molecular layer/cycle because the adsorbed source chemical molecules may be bulky or because substrate temperature affects the number of active sites (e.g. —OH groups) on the surface. It is well known that metal oxide thin films produced by ALD are uniform, have excellent adhesion and thus are firmly bonded to the substrate surface.
Experiments have revealed a drawback of the growth of metal thin films by an ALD type method. In the case of metal deposition it is difficult to attach source chemical molecules to the surface because essentially no active sites exist on the surface. The metal film grown is often non-uniform over an area of the substrate and it is easily peeled off from the surface, which indicates very poor adhesion of the film to the substrate.
Several attempts have been made to produce metal thin films by ALD type methods. Reproducibility of such an ALD metal growth process has traditionally been poor and the reactions do not take place at all on insulating surfaces like silicon oxide. There are publications about the ALD deposition of Cu metal by pulsing a copper compound, e.g. Cu(thd)2, on a surface and then reducing the Cu(thd)2 molecules bound to the surface into Cu with H2.
R. Solanki et al. (Electrochemical and Solid-State Letters 3 (2000) 479-480) have deposited copper seed layers by ALD. They deposited copper directly from alternate pulses of bis(1,1,1,5,5,5-hexafluoroacetylacetonato)copper(II)hydrate and either methanol, ethanol or formalin, i.e. a water solution of formaldehyde. The total pulsing cycle time was 64 s, i.e. slightly over one minute. Although the growth rate was not mentioned in the publication, a typical growth rate of a thin film made by ALD from metal β-diketonates is 0.03 nm/cycle due to the steric hindrance of the source chemical molecules. Thus, the deposition time for a 10-nm copper seed layer would be over 5 hours, which is uneconomical for wafer processing. A required minimum throughput of a wafer reactor is 10-12 wafers/hour. It is to be noted that according to Strem Chemicals, Inc. the decomposition temperature of the copper compound used by R. Solanki et al. is 220° C. R. Solanki et al. noticed copper film growth when the substrate temperature was 230-300° C. Therefore, partial thermal decomposition of copper source compound on substrate surface is probable.
One of the most advanced IC structures is the dual damascene structure which consists of a silicon substrate with transistors (source, gate and drain). Several electrically conducting layers are needed in the structure. The first metallization level is done with tungsten plugs and aluminium interconnects to prevent the contamination of the gate with copper. The remainder of the metallization levels are made of copper.
There are several ways of making dual damascene structures. An example of the process steps of a dual damascene process is described below.
Step 1. A silicon nitride etch stop is grown on the previous metallization surface.
Step 2. A via level dielectric is deposited.
Step 3. Another silicon nitride etch stop is deposited.
Step 4. A trench level dielectric is deposited. SiO2 has been favored as the dielectric material. Low-k materials such as nitrided silicon oxide and polymers have been experimented with as alternative dielectric materials.
Step 5. Patterning of dielectric by photolithography.

    
    
        a. A resist layer is deposited on dielectrics surface.
        b. The resist layer is patterned and the resist is removed from the via areas.
        c. Dielectrics are etched from the via areas with directional plasma. Etching terminates at the silicon nitride surface.
        d. Resist is stripped from the surface.
    
    


Step 6. Patterning of the etch stop layer by photolithography.

    
    
        e. A second resist layer is deposited on the surface.
        f. The resist layer is patterned and it is removed from the trench areas.
        g. Silicon nitride is removed with a short plasma nitride etch from the bottom of the holes that were made with the first plasma oxide etch.
        h. The second plasma oxide etch removes silicon dioxide from the exposed via and trench areas until the first silicon nitride etch stop is reached.
        i. The first silicon nitride etch stop is removed from the via bottom and the second silicon nitride etch stop from the trench bottom with a short plasma nitride etch.
        j. The resist is stripped from the substrate.
    
    


Step 7. A diffusion barrier layer is grown on all exposed surfaces.
Step 8. A seed layer for copper deposition is grown with CVD or PVD on the diffusion barrier layer.
Step 9. Vias and trenches are filled with copper by an electroplating process.
Step 10. The substrate surface is planarized with chemical mechanical polishing (CMP). The surface is polished until copper and a barrier layer are left only in trenches and vias.
Step 11. The surface is capped with a silicon nitride etch stop layer.
Step 12. The metallization process is then repeated for all the remaining metallization levels.
Alternatives for copper electroplating (Step 9) are electroless plating, physical vapor deposition (PVD) and chemical vapor deposition (CVD). A seed layer (c.f. Step 8) is typically needed for electroplating processes. Traditionally such a seed layer is deposited by chemical vapor deposition (CVD) or physical vapor deposition (PVD). In the electroplating process the substrate having an electrically conductive seed layer is immersed in a metal compound solution. The electrically conductive surface of the substrate is connected to an external DC power supply. A current passes through the substrate surface into the solution and metal is deposited on the substrate. The seed layer has high conductivity and it acts as a conduction and nucleation layer for the electroplating process. One can envision a seed layer that acts as a nucleation layer also for the CVD process. The seed layer carries current from the edge of the wafer to the center of the wafer and from the top surface of the wafer into the bottom of vias and trenches. A uniform and continuous seed layer is necessary to get uniform electroplated copper. Electrical contact is made to the seed layer. The quantity of the deposited metal is directly proportional to the local current density on the substrate.
The benefits of copper compared to aluminum are lower resistivity and better resistance to electromigration. Furthermore, since tighter packing density can be obtained with copper, fewer metallization levels are needed and the manufacturing costs are lower than with aluminum. With increasing aspect ratio it is becoming difficult to get sufficient step coverage for the seed layer with the state of the art technology.
In dynamic random access memories (DRAM), capacitors store data bits in the form of electrical charge. These memory capacitors must be recharged frequently due to the leaking of electrons. The simplest capacitor consists of two parallel metallic plates separated with a dielectric material. The capacity (C) of this plate capacitor depends according to equation (I) on the area (A) of the metallic plate, the distance (d) between the metallic plates and the dielectric constant (k) of the dielectric material. ε0 is the permittivity of space.

C=kε0A/d  (I)

Cylindrical capacitors are often used. The conductors are arranged coaxially. The charge resides on the inner wall of the outer conductor and on the outer surface of the inner conductor. In this case the capacitance (C) depends on the radius of the outer surface of the inner conductor (a), radius of the inner surface of the outer conductor (b), length of the cylinder (l) and dielectric constant (k) of the dielectric material between the conductors as shown in equation (II).

C=2πkε0l/ln(b/a)  (II)

The feature sizes in DRAMs are decreasing continuously. The capacitors must be made smaller in successive DRAM generation. In order to save surface area, planar capacitors are being replaced with vertical coaxial capacitors that may have aggressive aspect ratios. Decreasing the charge storing area means that the distance between the conductors must be decreased and/or the dielectric constant of the dielectric must be increased in order to keep the capacity sufficient. Decreasing the distance between the conductors causes voltage breakdown when the insulator thickness is too thin to hold the voltage.
Using high-k dielectrics, such as TiO2 and Ta2O5, resolves the above described problem related to decreasing feature size. However, high-k dielectrics create new problems, since they donate oxygen to the conductor and thus the capacitor properties deteriorate. Therefore, inert metals, such as platinum group metals, or conductive metal oxides, such as RuO2, must be used adjacent to the high-k metal oxides. But it is difficult to deposit thin films with good step coverage on new capacitor structures with small feature size and aggressive aspect ratio. As a conclusion, there is an increasing need for a method of producing conductive thin films with good step coverage and excellent thin properties such as adhesion to the substrate.
S.-J. Won et al. have presented a metal-insulator-metal (MIM) capacitor structure for giga-bit DRAMs (Technical Digest of the 2000 International Electron Devices Meeting (IEDM), San Francisco, Calif., Dec. 10-13, 2000). They used Ta2O5 as an insulator while the electrodes consisted of ruthenium which was deposited by CVD from Ru(EtCp)2 and gaseous oxygen at 300-400° C. Problems related to the method included poor step coverage and reaction speed sensitivity. When the nodes were made with 0.08 μm design rules, the step coverage dropped to 60%. The reaction of Ru(EtCp)2 with O2 was adversely affected by the partial pressures of the said compounds.
N+ or p+ doped polycrystalline silicon has been used as a gate electrode for transistors. However, several problems are associated with the use of poly-Si gate electrodes. In the case of boron doped p+ poly-Si, the diffusion of boron through the gate SiO2 destroys the electrical properties of the transistor. Poly-Si is thermodynamically unstable against high dielectric constant materials at high processing temperatures. In addition, poly-Si has rather high resistivity compared to metals. There is a tendency to replace the SiO2 gate oxide with a high dielectric constant metal oxide. A metal with appropriate work function would enable the tailoring of the CMOS threshold voltage. Refractory metals have been suggested for gate metals but the stability of the metal-gate oxide interface has been an issue. Platinum group metals are potential candidates for gate metals due to their inert nature. However, appropriate methods of depositing high-quality platinum group metal thin films for gate electrode applications have not yet been developed.
M. Utriainen et al. have demonstrated (Appl. Surf. Sci. 157 (2000) pp. 151-158) that ALD grown metal oxides can be used as interconnects in ICs after reducing the metal oxides into metals. They studied the direct ALD deposition of Cu, Ni and Pt and the indirect Ni growth method via reduction of NiO. However, they had problems with the quality of the nickel film: pinholes were formed on the thin films during the reduction of NiO with hydrogen gas.
SUMMARY OF THE INVENTION
Embodiments described herein provide methods of producing high quality conductive thin films with excellent step coverage, uniform thickness over a large area and excellent adhesion properties. The thin films may be used, for example, as seed layers for the electrodeposition of metal layers, and gate metals in thin film transistors and capacitors of advanced high-density integrated circuits.
The present method is applicable to the manufacture of conductive thin films, preferably comprising one or more of the following elements: rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver and gold.
According to one embodiment described herein, a method of forming a conductive thin film comprises depositing a metal oxide thin film on a substrate by an atomic layer deposition (ALD) process. The method further comprises at least partially reducing the metal oxide thin film by exposing the metal oxide thin film to an electric current, thereby forming a seed layer. In certain embodiments, the reduction of the metal oxide thin film essentially converts the metal oxide into an elemental metal seed layer that has sufficient conductivity to be used for subsequent electrochemical deposition.
According to another embodiment described herein, a method of producing a conductive thin film comprises the steps of (A) placing a substrate in a chamber and (B) exposing the substrate to a vapor phase first reactant. The first reactant adsorbs no more than a monolayer of metal species on the substrate. The method further comprises (C) removing excess first reactant from the chamber and (D) exposing the substrate to a second vapor phase reactant comprising a compound that is capable of oxidizing the adsorbed metal species on the substrate into metal oxide. The method further comprises (E) removing excess second reactant from the chamber and (F) repeating the above steps B through E at least three times to form a metal oxide film. The method further comprises (G) following step F, exposing the substrate to an electric current to reduce the metal oxide to metal.
According to still another embodiment described herein, a method of producing a conductive thin film comprises depositing a metal oxide thin film of at least 0.6 nm thickness on a substrate. The method further comprises reducing said metal oxide thin film to metal by exposing the metal oxide thin film to an electric current.
According to yet another embodiment described herein, a method of producing a conductive thin film comprises depositing a metal oxide thin film on a substrate by an atomic layer deposition (ALD) process. The method further comprises at least partially reducing the metal oxide thin film to elemental metal. In certain embodiments, the metal oxide thin film is at least partially reduced by exposing the metal oxide thin film to an electric current. In other embodiments, the metal oxide thin film is at least partially reduced by exposing the metal oxide thin film to one or more organic compounds that contain at least one functional group selected from the group consisting of —OH, —CHO, and —COOH.
According to another embodiment described herein, a method of producing a conductive thin film comprises depositing a metal oxide thin film on a substrate by an atomic layer deposition (ALD) process. The method further comprises at least partially reducing the metal oxide thin film to elemental metal in an electrochemical deposition tool.
Certain embodiments described herein are especially beneficial for making electrically conductive layers in structures that have high aspect ratios, like vias, trenches, local high elevation areas and other similar surface structures that make the surface rough and thin film processing complicated by conventional CVD and PVD methods. An ALD metal oxide process combined with a reduction step provides excellent step coverage of conductive thin films on all surface formations.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of the dual damascene structure.
FIG. 2 is a schematic view of a capacitor structure.
FIG. 3 is a schematic view of an NMOS transistor suitable for CMOS structures.
FIG. 4 depicts the electrical resistance of reduced copper samples.
FIG. 5 schematically illustrates a first cluster tool in accordance with embodiments of the present invention.
FIG. 6 schematically illustrates a second cluster tool in accordance with embodiments of the present invention.



DETAILED DESCRIPTION OF THE DRAWINGS
The dual damascene structure shown in FIG. 1 consists of a previous metallization layer 2 (e.g., Cu), an insulating layer 4 (e.g., SiO2), a via etch stop 6 (e.g., Si3N4), a via level insulator 8 (e.g., SiO2), a trench etch stop 10 (e.g., Si3N4), a trench level insulator 12 (e.g., SiO2), a diffusion barrier 14 (e.g., TaN), a seed layer 16 and a via/trench fill metal 18 (e.g., Cu).
The capacitor structure shown in FIG. 2 consists of a contact plug 30 (e.g., tungsten (W) or polysilicon), an insulator 32, an optional diffusion barrier 34 (e.g., TiN), a lower electrode 36 (e.g., Ru, Pt, or RuO2), a high-k dielectric film 38 (e.g., barium strontium titanate (BST)), and an upper electrode 40 (e.g., Ru or Pt).
The partial transistor structure shown in FIG. 3 consists of a substrate 60, an n-type well 62, a p-type diffusion region 64 (right drain, left source), a shallow trench isolation oxide 66, a gate dielectric 68, an optional barrier layer 70, a gate metal 72, a gate isolation spacers 74, and contact areas for tungsten plugs 76. The contact areas are dotted because they are not in the same vertical plane with the other numbered parts. A CMOS structure contains both PMOS and NMOS transistors. The contact areas against P-type semiconductor can be made of, e.g., Ni, and RuO. The contact areas against N-type semiconductor can be made of, e.g., Ru. Platinum can also be applied under W plugs. The choice of the metal or electrically conductive metal compound depends on the work function of the underlying layer and the reactivity of the surrounding materials with the said metal or electrically conductive metal compound.
FIG. 4 shows the resistance values of reduced copper samples. The values are the average of 10 measurements from each sample. ECD stands for copper metal deposited on silicon. ECD-1 and ECD-2 indicate pure ECD copper metals without any additional treatments. O-ECD-1 and O-ECD-2 indicate samples that have a copper oxide coating (about 350 nm). The rest of the samples had a copper oxide coating before the reduction experiments. N2 is nitrogen gas with a claimed purity of 99.9999%, MeOH is methanol, EtOH is ethanol, 2-PrOH is isopropanol, tert-BuOH is tert-butanol, PrCHO is butyraldehyde, Me2CO is acetone, HCOOH is formic acid, CH3COOH is acetic acid, and H2 is hydrogen. The number after the reagent name is the reaction temperature in degrees C. The number in parentheses is the reaction time in minutes.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
A layer of a low volatility oxide of a metal is grown on a substrate. Preferably the metal oxide is grown on the substrate according to the principles of an ALD process, and the following disclosure is directed to this embodiment. However, the skilled artisan will recognize that other methods of depositing a metal oxide thin film may be used in the methods of the invention. After the ALD process, the thin film consists essentially of a metal oxide or a mixture of metal oxides. The metal oxides are at least partially converted into a metal in a separate process step to increase the conductivity of the deposited oxide thin film. The conversion step can be done with any reducing agent capable of forming a stronger bond to oxygen than the metal to be reduced. Preferably, the reducing agent is in the gaseous phase. However, in the case of silver and gold oxides, the conversion step can be done simply by heating to decompose the oxide into metal and oxygen. In still other embodiments described herein, the reducing agent comprises an electric current applied to the metal oxide.
The following low volatility metal oxides and mixtures and nanolaminates of the following metal oxides are examples of compounds that are suitable for conversion into a conductive form by the method of certain embodiments: ReO2, Re2O5, ReO3, RuO2, OsO2, CoO, Co3O4, Rh2O3, RhO2, IrO2, NiO, PdO, PtO2, Cu2O, CuO, Ag2O (decomposes thermally at temperatures above 230° C.), Au2O3 (decomposes thermally at temperatures above 160° C.). However, a person skilled in the art will understand that embodiments described herein are not limited to these metal oxides, in part because the stoichiometry may vary in metal oxide films. In addition, the following high-volatility metal oxides exist: Re2O7, RuO4 and OsO4.
A metal oxide layer is preferably produced by the ALD process. A typical ALD process comprises the following steps:

    
    
        1. placing a substrate into a reaction chamber;
        2. feeding into the reaction chamber and contacting the substrate with a pulse of at least one first source chemical, preferably in the vapor phase, comprising a compound capable of adsorbing no more than a monolayer of metal species on the substrate;
        3. removing gases from the chamber;
        4. feeding into the reaction chamber and contacting the substrate with a pulse of at least one second source chemical, preferably in the vapor phase, comprising a compound capable of oxidizing the metal species on the substrate into a metal oxide, and
        4. removing gases from the chamber; and
        5. repeating steps 2 through 4 until a desired thickness of the growing thin film is reached.
    
    


According to the ALD principles, the previous reactant (i.e. previously pulsed source chemical) and the gaseous by-products of the surface reaction are removed from the reaction chamber before the next pulse of a reactant is introduced into the reaction chamber. The reactants and the by-products can be removed from the reaction chamber by pumping down the chamber to a higher vacuum by a vacuum pump, by purging the chamber with an inert gas pulse, or by a combination of the two.
In the methods of certain embodiments described herein, the ALD cycle described above is preferably repeated at least 3 times, more preferably at least 10 times. A metal oxide thin film of at least 0.6 nm is preferably formed on the substrate.
“Metal species” in the context of the present application means a separate molecule, atom or ion comprising one or more metal atoms.
According to one embodiment (FIG. 1), a substrate with open trenches and vias is provided into an ALD reaction chamber. A diffusion barrier layer 14 is on the surfaces of the substrate. The pressure of the reaction chamber is adjusted to about 5-10 mbar with a vacuum pump and flowing nitrogen gas. A metal oxide thin film is grown on the diffusion barrier 14 from alternate pulses of a metal source chemical and oxygen source chemical. Surplus source chemical and reaction by-products are essentially removed from the reaction chamber after each source chemical pulse before the next source chemical pulse is introduced into the reaction chamber and contacted with the substrate surface. The pulsing cycle is repeated until the thickness of the metal oxide film is sufficient for seed layer purposes. The metal oxide film is reduced into a metal layer and used as a seed layer 16 for an electroplating process.
According to a second embodiment (FIG. 2), a substrate is provided into a reaction chamber of an ALD reactor. The substrate is heated to a deposition temperature of selected metal oxide. Alternate gas phase pulses of a metal source chemical and an oxygen source chemical are introduced into the reaction chamber and contacted with the substrate surface. A metal oxide film is grown on the surface. The metal oxide is used as the first electrode 36 of a capacitor or converted into corresponding metal and used as the first electrode 36 of the capacitor. Then a thin film of a high-k dielectric material 38 is grown on the first electrode 36. The high-k layer 38 is optionally annealed. A metal oxide thin film is grown by ALD on the high-k layer. The metal oxide film is converted into corresponding metal and used as the second electrode 40 of a capacitor. However, the metal oxide thin film can be used as the second electrode of the capacitor if the conductivity of the metal oxide thin film is sufficiently high. In certain embodiments, the metal oxide thin film is used as the second electrode when its resistivity is preferably less than about 500 μΩ-cm, more preferably less than about 300 μΩ-cm, and most preferably less than about 100 μΩ-cm. An example of a suitable metal oxide is ruthenium dioxide (RuO2) that has a resistivity of about 35 μΩ-cm.
According to a third embodiment (FIG. 3), a substrate is provided into a reaction chamber of an ALD reactor. The surface may be, for example, a transistor gate oxide 68 or doped silicon on source and drain areas 64. The substrate is heated to a deposition temperature. Alternate gas phase pulses of a metal source chemical and an oxygen source chemical are introduced into the reaction chamber and contacted with the substrate surface. Metal oxide film is grown on the surface. The metal oxide is used as the gate electrode of a transistor as such or converted into the corresponding metal and used as the gate electrode of a transistor. The metal is also used as an intermediate layer 76 between silicon and tungsten plugs on the source and the drain areas of the transistor.
According to one embodiment described herein, the metal oxide is ruthenium oxide and one deposition cycle of ruthenium oxide consists of a ruthenium halide pulse, nitrogen purge, a pulse of a reducing agent, nitrogen purge, an oxygen source pulse and nitrogen purge. It is known that RuF6 and RuF5 can be reduced with iodine into RuF4 (N. N. Greenwood A. Earnshaw in “Chemistry of the Elements”, Pergamon Press, 1984, p. 1258). When, e.g., RuF5 chemisorbs on a surface, Ru should release at least one F and form a bond to the surface. Equation (III) illustrates the reaction.

RuF5(g)+—OH(ads.)→—O—RuF4(ads.)+HF(g)  (III)

The oxidation state of Ru in RuF5 is +5, which is too high for the formation of RuO2. According to one embodiment described herein, Ru(V) compound that is adsorbed on a surface is reduced into Ru(IV) compound with gaseous iodine. After the reduction process the oxidation state of ruthenium in the adsorbed Ru compound is +4 and results in the growth of RuO2 when a pulse of oxygen source chemical is introduced into the reactor and contacts the surface of the substrate. Equations (IV) and (V) illustrates the reactions:

10(—RuF4)(ads.)+I2(g)→10(—RuF3)(ads.)+2IF5(g)  (IV)

When an oxygen source chemical is contacted with the surface a reaction according to equation (V) takes place:

2(—RuF3)(ads.)+4H2O(g)→2[—RuO(—OH)](ads.)+6HF(g)  (V)

Due to equal oxidation states of Ru in the adsorbed Ru source compound and Ru in the resulting ruthenium oxide, the removal of F ligands from the surface in the form of gaseous HF molecules is a straightforward procedure.
According to one embodiment described herein, the metal oxide thin film deposited by ALD consists of metallic ruthenium and ruthenium oxide. The growth of the ruthenium-rich film is based on reduction-oxidation (redox) reactions on the surface.
Known oxides of ruthenium are RuO2 and RuO4. The vapor pressure of RuO2 is negligible at the reactor temperatures used according to certain embodiments described herein. However, RuO4 has such a high vapor pressure, 760 torr at 40° C., that it can easily be evaporated from an external source.
One deposition cycle for the growth of ruthenium-rich thin film consists of a RuO4 pulse, a nitrogen purge, a pulse of vaporized organic reducing agent, and a nitrogen purge. Therefore, in the beginning of the growth process ruthenium tetra-oxide (RuO4) is adsorbed on the substrate surface. Adsorbed ruthenium oxide is reduced to metallic ruthenium with an organic reducing agent, ruthenium tetra-oxide is contacted again with the surface of the substrate when RuO2 is formed and then RuO2 is at least partly reduced with an organic reducing agent to metallic ruthenium.
Ruthenium metal is in the oxidation state of 0, while ruthenium has an oxidation state of VIII in RuO4. On the substrate surface there is ruthenium with low oxidation state. High oxidation state ruthenium source chemical is contacted with the surface. A reduction-oxidation (redox) reaction according to equation (VI) takes place on the substrate surface:

Ru(ads.)+RuO4(g)→2RuO2(ads.)  (VI)

In addition, one molecular layer of RuO4 may adsorb on the low-volatility RuO2 surface.
Then the surface is treated with a reducing agent pulse:

RuO2(ads.)+2CH3CH2OH→Ru(ads.)+2CH3CHO(g)+2H2O(g)  (VII)

Suitable reducing agents include alcohols, aldehydes, carboxylic acids and hydrogen radicals.
Ruthenium metal thin film and/or ruthenium oxide thin film produced thereof can be used as a seed layer and/or an electrode.
Deposition of ternary ruthenium compounds is also possible. For example, SrRuO3, which is suitable electrode material, is grown by ALD by applying alternate source chemical pulses of a Sr compound, Ru compound and oxygen compound.
According to one embodiment described herein, OsO4 is prepared in situ with a highly reactive oxygen compound from low volatility Os metal or osmium oxides such as OsO2. OsO4 requires careful handling due to its high toxicity and volatility (vapour pressure is 760 torr at 130° C.). A low-volatility Os source is placed in a zone in front of the substrate space. The source is heated to about 130-150° C. Then, e.g., ozone is pulsed over Os.

Os(s)+4O3(s)→OsO4(g)+4O2(g)  (VII)

Surplus O3 gas is decomposed into O2 before the reaction chamber to protect the OsO2 layer that is growing on the substrate surface. O3 is easily decomposed by heating or with molecular sieves such as zeolites.
When depositing silver and gold oxides by ALD, special attention has to paid to the selection of growth temperatures, since Ag2O decomposes into Ag and O2 at temperatures above 230° C. and Au2O3 decomposes into Au and O2 at temperatures above 160° C. Therefore, the deposition temperature of silver oxide is preferably kept below 230° C. and the deposition temperature of gold oxide is preferably below 160° C.
The Source Chemicals
The ALD source chemicals must have sufficient volatility at the source temperature. The vapor pressure of the source chemical should be at least about 0.02 mbar at the source temperature to enable reasonably short pulse times for saturating the substrate surfaces. The metal source chemicals must be thermally stable at the deposition temperature to prevent particle formation in the gas-phase of the reaction chamber.
Suitable metal source compounds are sold, for example, by Strem Chemicals, Inc. (7 Mulliken Way, Dexter Industrial Park, Newburyport, Mass., USA) and Tri Chemical Laboratory, Inc. (969 Helena Drive, Sunnyvale, Calif., USA).
Low oxidation state rhenium oxide can be grown by ALD for example from following rhenium compounds:

    rhenium(VII)oxide (Re2O7), rhenium pentacarbonyl chloride (Re(CO)5Cl), methyltrioxorhenium(VII) (CH3ReO3), cyclopentadienylrhenium tricarbonyl ((C5H5)Re(CO)3), pentamethylcyclopentadienylrhenium tricarbonyl ([(CH3)5C5]Re(CO)3), and i-propylcyclopentadienylrhenium tricarbonyl ((C3H7)C5H4Re(CO)3).


Low oxidation state ruthenium oxide can be grown by ALD for example from following ruthenium compounds:

    ruthenium(VII)oxide (RuO4), bis(cyclopentadienyl)ruthenium ((C5H5)2Ru), bis(pentamethylcyclopentadienyl)ruthenium ([(CH3)5C5]2Ru), cyclopentadienylruthenium dicarbonyl ((C5H5)2Ru(CO)2), bis(2,2,6,6-tetramethyl-3,5-heptanedionato)(1,5-cyclooctadiene)ruthenium(II) (C11H19O2)2(C8H12)Ru, tris(dipivaloylmethanato)ruthenium i.e. tris(2,2,6,6-tetramethyl-3,5-heptanedionato)ruthenium (Ru(DPM)3 or Ru(thd)3), anhydrous rutheniumnitrate (Ru(NO3)3), and anhydrous ruthenium (III) nitrosyl nitrate (Ru(NO)(NO3)3).


Low oxidation state osmium oxide is preferably grown by ALD for example from following osmium compounds:

    bis(cyclopentadienyl)osmium ((C5H5)2Os), bis(pentamethylcyclopentadienyl)osmium ([(CH3)5C5]2Os), and osmium(VIII)oxide (OsO4).


Cobalt oxide is preferably grown by ALD for example from following cobalt compounds:

    bis(cyclopentadienyl)cobalt(II) ((C5H5)2Co), bis(methylcyclopentadienyl)cobalt(II) ((CH3C5H4)2Co), bis(pentamethylcyclopentadienyl)cobalt(II) ([(CH)3C5]2Co), cobalt tricarbonyl nitrosyl (Co(CO)3NO), cyclopentadienylcobalt dicarbonyl C5H5Co(CO)2, cobalt(III)acetylacetonate (Co(CH3COCHCOCH3)3), tris(2,2,6,6-tetramethyl-3,5-)cobalt(III) i.e. tris(dipivaloylmethanato)cobalt (Co(TMHD)3, or Co(DPM)3, or Co(thd)3, or Co(C11H19O2)3), and anhydrous cobalt nitrate (Co(NO3)3), the synthesis of which has been described by R. J. Logan et al. in J. Chem. Soc., Chem. Commun. (1968) 271.


Rhodium oxide is preferably grown by ALD for example from following rhodium compounds:

    2,4-pentanedionatorhodium(I)dicarbonyl (C5H7Rh(CO)2), tris(2,4-pentanedionato)rhodium rhodium(III)acetylacetonate (Rh(C5H7O2)3), and tris(trifluoro-2,4-pentanedionato)rhodium.


Iridium oxide is preferably grown by ALD for example from following iridium compounds:

    (methylcyclopentadienyl)(1,5-cyclooctadiene)iridium(I) ([(CH3)C5H4](C8H12)Ir) and trisallyliridium ((C3H5)3Ir).


Nickel oxide is preferably grown by ALD for example from following nickel compounds:

    nickel carbonyl (Ni(CO)4), bis(2,2,6,6-tetramethyl-3,5-heptanedionato)nickel(II) (Ni(DPM)2, or Ni(thd)2, or Ni(C11H19O2)2), nickel(II)acetylacetonate, also known as bis(2,4-pentanedionato)nickel(II), nickel(II)trifluoroacetylacetonate, nickel(II)hexafluoroacetylacetonate (Ni(CF3COCHCOCF3)2), nickel(II)dimethylglyoxime (Ni(HC4H6N2O2)2), and tetrakis(trifluorophosphine)nickel(0) (Ni(PF3)4).


Palladium oxide is preferably grown by ALD for example from following palladium compounds: Pd(thd)2 and bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)palladium (Pd(CF3COCHCOCF3)2).
Platinum oxide is preferably grown by ALD for example from following platinum compounds:

    platinum(II)hexafluoroacetylacetonate (Pt(CF3COCHCOCF3)2), (trimethyl)methylcyclopentadienylplatinum(IV) ((CH3)3(CH3C5H4)Pt), and allylcyclopentadienylplatinum ((C3H5)(C5H5)Pt).


Copper oxide is preferably grown by ALD for example from the following copper compounds and their derivatives:

    CuCl, CuBr, CuI, bis(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)copper(II) (Cu(FOD)2), bis(2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II) (Cu(TMHD)2, or Cu(DPM)2, or Cu(thd)2), copper(II)acetylacetonate (Cu(CH3COCHCOCH3)2), also known as Cu(acac)2, derivatives of Cu(acac)2 such as alkyl derivatives of Cu(acac)2, copper(II)trifluoroacetylacetonate (Cu(CF3COCHCOCH3)2), copper(II)hexafluoroacetylacetonate (Cu(CF3COCHCOCF3)2), hexafluoroacetylacetonatocopper(I)trimethylphosphine adduct (Cu(CF3COCHCOCF3)P(CH3)3), copper(II)dialkylaminoalkoxides such as copper(II)dimethylaminoethoxide, cyclopentadienylcopper(I)triethylphosphine ((C5H5)Cu:P(C2H5)3), ethylcyclopentadienylcopper triphenylphosphine adduct ((C2H5C5H4)Cu:P(C6H5)3), hexafluoroacetylacetonatocopper(I)triethylphosphine adduct ((C5HF6O2)Cu:P(C2H5)3), hexafluoroacetylacetonatocopper(I)2-butyne adduct ((C5HF6O2)Cu:CH3C≡CCH3), hexafluoroacetylacetonatocopper(I)1,5-cyclooctadiene adduct ((C5HF6O2)Cu:C8H12), hexafluoropentanedionatocopper(I)vinyltrimethylsilane adduct, and anhydrous copper nitrate (Cu(NO3)2), the synthesis of which has been described by C. C. Addison et al. (J. Chem. Soc. (1958) pp. 3099-3106).


Silver oxide is preferably grown by ALD for example from hexafluoroacetylacetonatosilver trimethylphosphine adduct ((C5HF6O2)Ag:P(CH3)3).
Gold oxide is preferably grown by ALD for example from following gold compounds:

    gold(III)fluoride AuF3, dimethyl(acetylacetonato)gold(III) ((CH3)2(C5H7O2)Au), and dimethylhexafluoroacetylacetonatogold ((CH3)2Au(C5HF6O2)).


The oxygen source material used in the method of certain embodiments is selected from a group of volatile or gaseous compounds that contain oxygen and are capable of reacting with an adsorbed metal compound on the substrate surface, at the deposition conditions, resulting in growth of metal oxide thin film on the substrate surface.
It is to be noted that Re, Ru and Os form highly volatile oxides when reacting with strong oxidizing agents. It is therefore necessary to exclude strong oxidizing agents from the vicinity of the substrate when growing lower oxidation state oxides of Re, Ru and Os.
In the production of a metal oxide thin film on a wafer the oxygen source chemical is selected for example from a group consisting of water (H2O), hydrogen peroxide (H2O2), oxygen (O2), ozone (O3), singlet oxygen 1O2, and oxygen compounds with unpaired electrons, as well as oxygen radicals and OH radicals.
A special group of oxygen source chemicals can be used when the metal source chemical is an anhydrous metal nitrate. This group of oxygen chemicals consists of an aqueous solution of ammonia (NH3*H2O or NH4OH), an aqueous solution of hydroxylamine (NH2OH*H2O), and an aqueous solution of hydrazine (N2H4*H2O).
Mixtures of at least two oxygen source chemicals can also be used for metal oxide deposition. Especially in case of ozone, the substrate surface may remain too “dry” (i.e. the surface contains too few —OH groups) and the number of active surface sites (especially —OH groups) will drop below an optimum value. By adding certain amount of water vapor to the ozone pulse, the number of —OH groups on the surface can be increased and the growth rate of the metal oxide thin film can be improved. Also water vapor can be pulsed after the O3 pulse to achieve the same result as with the water-ozone pulse.
Reduction Process
According to certain embodiments described herein, the metal oxide thin film that is to be reduced into a metal thin film consists essentially of a metal oxide or a mixture of metal oxides. The method of reducing the metal oxide layer plays a very important role in certain embodiments described herein. The metal oxide is reduced in certain embodiments by means of volatile organic reducing agents, such as organic compounds that contain at least one —OH, —CHO and/or —COOH functional group or gaseous mixtures of said organic compounds. Surprisingly, good adhesion of the reduced metal oxide thin film is preserved when the above mentioned organic reducing agents are used. In comparison, the use of very strong reducing agents, such as hydrogen plasma, causes damage to the underlying films and may result in harmful hydride incorporation in the film at higher temperatures and variable adhesion between films. In other embodiments, the reducing agent comprises an electric current applied to the metal oxide thin film.
Chemical Reducing Agents
In certain embodiments, the conversion step is preferably done with a reducing agent capable of forming a stronger bond to the oxygen of the metal oxide layer than the metal in the said oxide layer. In certain embodiments, the reduction can be performed by introducing the reducing agent into the electrochemical deposition (ECD) tool as is used for subsequent metal deposition. In addition, the chemical reducing agent can be used in the ECD tool, especially in electroless plating tools. In certain other embodiments, the reducing agent is in gaseous form. The gaseous reducing agent is capable of taking away the oxygen that was bound to the metal oxide and thus an elemental metal is left on the substrate surface. For example, primary alcohols react into aldehydes and a water molecule is released as a byproduct. Aldehydes take one oxygen atom and react into carboxylic acids, without the formation of a water molecule.
According to one embodiment described herein, reducing agents that comprise relatively bulky molecules (alcohols, aldehydes and carboxylic acids) are used. Bulky source chemical molecules do not easily diffuse inside the metal oxide film. Thus the reduction reaction takes place only at the surface of the metal oxide layer. During the reduction process, oxygen ions diffuse towards the surface where oxygen is depleted by the reducing chemicals. Gaseous by-products are thus not formed inside the film, but only on the surface. The structural integrity of the forming metal film is thereby preserved and the formation of pinholes on the film will be avoided.
The reduction process of such embodiments is preferably carried out in a reaction space that enables controlled temperature, pressure and gas flow conditions. The organic reducing agent is preferably vaporized and fed to the reaction space, optionally with the aid of an inert carrier gas, such as nitrogen. The reducing agent is contacted with the substrate, whereby the metal oxide layer is reduced at least partly to metal and the reducing agent is oxidized. Typically, the reaction space is then purged with an inert carrier gas to remove the unreacted organic reducing agent and reaction products.
The reduction process according to certain embodiments is preferably carried out at low temperatures. Theoretically, the reactions between oxide(s) and the reducing agents used in the process of certain embodiments are favorable in a wide temperature range, even as low as room temperature. Kinetic factors and the diffusion rate of oxygen to the thin film surface set a lower limit on the actual process temperatures that can be applied successfully. The temperature in the reaction space is preferably in the range of 200° C. to 400° C., more preferably 300° C. to 400° C. and even more preferably 310° C. to 390° C. It is to be noted that in case of very thin metal oxide films, the reduction temperature can be even lower than 250° C. If the deposition and reduction temperature are very low, thus causing a slow reduction reaction or slow diffusion of oxygen through the metal oxide layer, the deposition of the metal film can be divided into at least two parts to speed up the total processing time. One layer of the metal oxide, preferably comprising more than one monolayer, is deposited by ALD, then reduced into a metal layer, another layer, preferably comprising more than one monolayer of the metal oxide, is deposited by ALD, then reduced into a metal layer, et cetera, until a metal film of desired thickness is obtained.
In case of electrochemical reduction, the reduction temperature is preferably between about 0° C. and about 100° C., more preferably between about 20° C. and about 80° C. and most preferably between about 50° C. and about 60° C.
The pressure in the reaction space is preferably 0.01 to 20 mbar, more preferably 1 to 10 mbar.
The processing time varies according to the thickness of the layer to be reduced. A layer of copper oxide having a thickness up to 300-400 nm can be reduced in approximately 3 to 5 minutes. For layers having a thickness of approximately 0.1-10 nm, the processing time is in the order of seconds. Preferably the layer to be reduced has a thickness of at least 0.6 nm.
The organic compounds used in the reduction according to certain embodiments described herein preferably have at least one functional group selected from the group consisting of alcohol (—OH), aldehyde (—CHO), and carboxylic acid (—COOH).
Suitable reducing agents containing at least one alcohol group are preferably selected from the group consisting of:

    
    
        primary alcohols which have an —OH group attached to a CH3 group (CH3OH) or to a carbon atom which is bonded to one other carbon atom, in particular primary alcohols according to the general formula (I)

R1—OH  (I)

         wherein R1 is a linear or branched C1-C20 alkyl or alkenyl group, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl,
         examples of preferred primary alcohols being methanol (CH3OH), ethanol (CH3CH2OH), propanol (CH3CH2CH2OH), butanol (CH3CH2CH2CH2OH), 2-methyl propanol ((CH3)2CHCH2OH) and 2-methyl butanol (CH3CH2CH(CH3)CH2OH),
        secondary alcohols which have an —OH group attached to a carbon atom which is bonded to two other carbon atoms, in particular secondary alcohols according to formula (II)
    
    






    
    
         wherein each R1 is selected independently from the group of linear or branched C1-C20 alkyl and alkenyl groups, preferably methyl, ethyl, propyl, butyl, pentyl and hexyl, examples of suitable secondary alcohols being 2-propanol ((CH3)2CHOH) and 2-butanol (CH3CH(OH)CH2CH3),
        tertiary alcohols which have an —OH group attached to a carbon atom which is bonded to three other carbon atoms, in particular tertiary alcohols according to the general formula (III)
    
    






    
    
         wherein each R1 is selected independently from the group of linear or branched C1-C20 alkyl and alkenyl groups, preferably methyl, ethyl, propyl, butyl, pentyl and hexyl, an example of suitable tertiary alcohol being tert-butanol ((CH3)3COH),
        polyhydroxy alcohols, such as diols and triols, which can have primary, secondary and/or tertiary alcohol groups as presented above, for example ethylene glycol (HOC2CH2OH) and glycerol (HOCH2CH(OH)CH2OH),
        cyclic alcohols which have an —OH group attached to at least one carbon atom which is part of a ring of 1-10, typically 5-6 carbon atoms,
        aromatic alcohols having at least one —OH group attached either to the benzene ring or to a carbon atom in a side-chain, such as benzyl alcohol (C6H5CH2OH), o-, p- and m-cresol and resorcinol,
        halogenated alcohols, preferably having the general formula (IV)

CHXnX3−n—R2—OH  (IV)

         wherein X is F, Cl, Br or I, preferably F or Cl,
        
            n is an integer from 0 to 2, and
             R2 is selected from the group of linear or branched C1-C20 alkylene and alkenylene groups, preferably methylene, ethylene, trimethylene, tetramethylene, pentamethylene and hexamethylene, and in particular methylene and ethylene,
        
        
         an example of a suitable compound is 2,2,2-trifluoroethanol (CF3CH2OH), and
        other derivatives of alcohols, for example amines, such as methyl ethanolamine (CH3NHCH2CH2OH).
    
    


Suitable reducing agents containing at least one —CHO group are preferably selected from the group consisting of

    
    
        compounds having the general formula (V)

R3—CHO  (V)

         wherein R3 is hydrogen or linear or branched C1-C20 alkyl or alkenyl group, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl, in particular methyl or ethyl, examples of suitable compounds according to formula (V) are formaldehyde (HCHO), asetaldehyde (CH3CHO) and butyraldehyde (CH3CH2CH2HO),
        alkanedial compounds having the general formula (VI)

OHC—R4—CHO  (VI)

         wherein R4 is a linear or branched C1-C20 saturated or unsaturated hydrocarbon, but it is also possible that R4 is zero, i.e., the aldehyde groups are bonded to each other,
        halogenated aldehydes, and
        other derivatives of aldehydes.
    
    


Suitable reducing agents containing at least one —COOH group are preferably selected from the group consisting of

    
    
        compounds having the general formula (VII)

R5—COOH  (VII)

         wherein R5 is hydrogen or linear or branched C1-C20 alkyl or alkenyl group, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl, in particular methyl or ethyl, examples of suitable compounds according to formula (VI) being formic acid (HCOOH) and acetic acid (CH3COOH),
        polycarboxylic acids,
        halogenated carboxylic acids, and
        other derivatives of carboxylic acids.
    
    


Reactors used for deposition of thin films by ALD and/or CVD are preferably used in the methods of certain embodiments described herein. However, the deposition of the metal oxide thin film and the reduction step in embodiments using chemical reduction agents are preferably carried out sequentially in one reactor. The reduction process can also be done in a cluster tool where the substrate arrives from a previous process step, the substrate is treated with the reducing agent and finally transported to the following process step. In a cluster tool the reaction space temperature can be kept constant, which improves the throughput when compared to a reactor which is heated to the process temperature before each run.
Electric Current as Reducing Agent
In certain embodiments, the deposited metal oxide thin film is reduced by exposing it to an electric current. In certain such embodiments, the electric current is generated by placing the substrate in an electrochemical deposition (ECD) or electrochemical mechanical deposition (ECMD) tool, such as the NuTool 2000TM tool available from NuTool, Milpitas, Calif., USA. Reduction of the metal oxide thin film to a metal thin film can create a seed layer for subsequent layer formation using electrochemical deposition or electroless deposition. In certain embodiments, the reduction can be performed in the same ECD tool as is used for subsequent metal deposition.
In an exemplary embodiment, a conformal copper oxide (CuO) film is deposited by ALD on a barrier film. Suitable barrier films for copper include, but are not limited to, TiN, TaN and WNC. The CuO film has a thickness preferably at least 0.6 nanometers, more preferably between approximately 1 nanometer and approximately 20 nanometers, and most preferably between approximately 1 nanometer and approximately 3 nanometers.
Electric current can be used as the reducing agent for the CuO film by using the following reactions:

CuO(s)+H2O+2e−→Cu(s)+2OH−

2OH−→2OH+2e−

2OH→H2O+1⁄2O2(g).

These reactions can be used to normally reduce native CuO in ECD tools, and can also be used to reduce the ALD-generated CuO film which is deposited on a conductive barrier film layer. The resultant Cu film can then be used as a seed layer in an ECD tool for subsequent metal layer formation. In certain embodiments, the seed layer has a resistivity of preferably between about 1 μΩ-cm and about 30 μΩ-cm, more preferably between about 1.67 μΩ-cm and about 10 μΩ-cm, and most preferably between about 1.7 μΩ-cm and about 3 μΩ-cm. Resulting structures can be used in microchip metallization such as single and dual damascene processes.

In certain embodiments, the electrolyte solution preferably comprises water-soluble metal hydroxide such as alkali metal hydroxide, e.g. sodium hydroxide, dissolved in purified water. Metal hydroxide increases the pH of the solution so that copper oxide does not dissolve from the surface into the solution. Hydroxyl ions act as charge and oxygen carriers in the solution. In certain embodiments, the electric current is applied at temperatures preferably between about 0° C. and about 100° C., more preferably between about 20° C. and about 80° C., and most preferably between about 50° C. and about 60° C. In certain embodiments, the electric current is applied for a time period of preferably between about 1 second and about 3600 seconds, more preferably between about 30 seconds and about 1000 seconds.
Preferably, the subsequent metal layer formation is performed using the same ECD tool as is used for reducing the CuO film. An exemplary ECD tool comprises two or more ECD modules so that one ECD module contains alkaline solution for the copper oxide reduction and one ECD module contains acidic solution for the copper metal deposition. An example of such a tool is LuminaCuTM system available from NuTool, Milpitas, Calif., USA. In addition, prior to the formation of the subsequent metal layer using ECD, the resulting Cu seed layer can be repaired using known seed repair technologies, such as electroless deposition processes (see, e.g., Peter Singer, “Progress in Copper: A Look Ahead,” Semiconductor International, May 1, 2002, the disclosure of which is incorporated in its entirety by reference herein). The basics of electroless deposition, also known as electroless plating, have been presented by G. Mallory and J. Hadju in “Electroless Plating: Fundamentals and Applications”, Noyes Publications, 1990, which is also included in its entirety by reference herein.
Using the same ECD tool to reduce the ALD-generated metal oxide films into seed metal films and to form the subsequent metal layers avoids the necessity of an additional gas-phase reduction module, thereby saving time and money. ECD tools have small footprints, so using ECD tools for reduction also saves floor space in the clean room for more ALD modules for forming the barrier layers and CuO layers in the same metallization cluster.
Nickel oxide (NiO), silver oxide (AgO), cobalt oxide (CoO) and ruthenium oxide (RuO2) serve as examples of other metal oxides with which ECD can be used.
A surprising finding related to certain embodiments described herein is that the film has very good adhesion to the substrate, even after a reduction step. The structural integrity of the metal film is preserved and the formation of pinholes in the film is avoided. While the exact nature of the interface between the metal film and the substrate is unclear, it is obvious that the interface is much stronger than in the case of direct deposition of metal films by ALD.
ALD-grown metal oxides are denser than PVD- or CVD-grown metal oxides. It would be logical to assume that it is difficult to apply any electrochemical reduction or deposition processes on surfaces that have dense structure and poor electrical conductivity. A surprising finding related to certain embodiments described herein is that the electrochemical reduction process could successfully be applied to the reduction of dense ALD-grown metal oxides that are poor electrical conductors before the reduction process.
EXAMPLES
Example 1
ALD of Copper Oxide, Method I
The deposition was carried out in an F-200 ALCVDTM reactor manufactured by ASM Microchemistry Oy, Finland. Cu(thd)2 was loaded into an external source container and heated to 180° C. The flow of the O3/O2 mixture was set to 120 std.cm3/min. There was about 15% of O3 in O2. A 200 mm silicon wafer was loaded through a load lock into the reaction chamber of the reactor. The pressure of the reaction chamber was adjusted to about 5-10 mbar with a vacuum pump and flowing nitrogen gas. The reaction chamber was then heated to 210° C. One pulsing cycle consisted of 0.5 s Cu(thd)2 pulse, 1.0 s N2 purge, 0.5 s O3 pulse and 1.0 s N2 purge. The pulsing cycle was repeated 3000 times. The thin film grown on the wafer had a brownish gray color, high resistivity and excellent adhesion. The thin film consisted of CuO, which was treated with an organic reducing agent to create a metallic copper metal film on the wafer. The reduced thin film had good conductivity and showed excellent adhesion to the substrate.
Example 2
ALD of Copper Oxide, Method II
The deposition of copper oxide was carried out according to Example 1, with CuCl used as the copper source chemical. Pieces of silicon substrates with and without a TiN coating were loaded into the reaction chamber of the reactor. CuCl was loaded into a source tube and the reactor was evacuated. The pressure of the reaction chamber was adjusted to about 3-10 mbar with a vacuum pump and flowing N2 gas. The reaction chamber was heated to 380° C. and CuCl to about 360° C. Copper oxide grew in a controlled manner and with excellent adhesion to both of the substrates and had the same performance as the CuO film obtained in Example 1.
Example 3
ALD of Copper Oxide, Method III
Surprisingly, it was found that copper oxide (Cu2O) can be grown by ALD using anhydrous copper nitrate Cu(NO3)2 and an aqueous solution of NH3 as source chemicals. It turned out that dry gaseous ammonia does not form Cu2O with anhydrous copper nitrate.
Cu(NO3)2 was synthesized according to the instructions of C. C. Addison et al. (J. Chem. Soc. (1958) pp. 3099-3106). Wet NH3 vapour was formed by evaporating aqueous solution of NH3 at room temperature from an external source bottle. The temperature of the Cu(NO3)2 source tube was set to 120° C. Silicon and TiN-coated silicon were used as substrates. The substrate temperature was about 150° C. Higher substrate temperatures were also tested. However, it was found that it is difficult to control the film uniformity at higher growth temperatures, possibly because of the thermal decomposition of copper nitrate in gas phase.
One pulsing cycle consisted of four steps, in the following order: Cu(NO3)2 pulse (1.0 s), N2 purge (2.0 s), NH3*H2O pulse (2.0 s), N2 purge (2.0 s).
The thin film grown at 150° C. on the substrate had a growth rate of 0.2 Å/cycle and according to EDS measurements consisted of Cu2O.
Example 4
ALD of Copper Oxide, Method IV
The deposition was carried out in an Pulsar® 2000 ALCVDTM reactor manufactured by ASM America, Inc., USA. Cu(acac)2 was loaded into an external source container and heated to a temperature that was selected from a range of 130-180° C. The flow rate of the O3/O2 mixture was programmed to 200 std.cm3/min (sccm). There was about 15% of O3 in O2. A 200-mm silicon wafer was loaded through a load lock into the reaction chamber of the reactor. The pressure of the reaction chamber was adjusted to about 5-10 mbar with a vacuum pump and flowing nitrogen gas. The reaction chamber was then heated to a temperature that was selected from a range of 135-190° C., preferably to 135° C. One pulsing cycle consisted of 0.5 s Cu(acac)2 pulse, 1.0 s N2 purge, 1.0 s O3 pulse and 1.0 s N2 purge. The pulsing cycle was repeated 1000 times. The thin film grown on the wafer had a brownish gray color, high resistivity and excellent adhesion. The thin film consisted of CuO, which was treated with an organic reducing agent ethanol to create a metallic copper metal film on the wafer. The reduced thin film had good conductivity and showed excellent adhesion to the substrate.
Example 5
ALD of Cobalt Oxide
Co(thd)3 and O3 were used as source chemicals for the cobalt oxide deposition. Co(thd)3 was heated to 110° C. O3 was prepared from 99.9999% O2 with an external ozone generator. The resulting oxygen source gas mixture consisted of 10-20 vol.-% O3 in O2. Nitrogen, evaporated from liquid nitrogen, was used as an inert purging gas. Co(thd)3 pulse length varied from 1.5 s to 2.0 s, while O3 pulse (flow rate 100 std.cm3/min) length varied from 2.0 s to 4.0 s. Silicon was used as the substrate material. Substrate temperatures between 150° C. and 350° C. were tested. One pulsing cycle consisted of four sequential steps: Co(thd)3 pulse, N2 purge, O3 pulse, N2 purge.
The higher deposition temperature tested resulted in uncontrolled film growth, as Co(thd)3 decomposed thermally thus producing a poor thickness profile for the thin film. At the lower substrate temperatures, a controlled growth rate of the thin film (0.3 Å/cycle) and good adhesion were obtained. A total of 2000 pulsing cycles resulted in a 64 nm thick cobalt oxide layer. According to Energy Dispersive X-ray Spectroscopy (EDS) measurements the thin films consisted of CoO.
Example 6
ALD of Palladium Oxide
Substrates with Si, TiN, WN, W3C and SiO2 surfaces were loaded into an F-120 ALCVDTM reactor manufactured by ASM Microchemistry Ltd., Finland. Pd(thd)3 was loaded to a solid source tube of the reactor. The reactor was pumped to vacuum. The pressure of the reaction chamber was adjusted to about 5-10 mbar with flowing nitrogen gas while the pumping of the reactor continued. The Pd(thd)3 was heated to 110° C. and the reaction chamber to 150° C.
One pulsing cycle consisted of four steps in the following order: Pd(thd)3 pulse (2.0 s), N2 purge (1.0 s), O3 pulse (4.0 s), N2 purge (2.0 s).
The growth rate of palladium oxide from Pd(thd)3 and O3 was 0.15 A/cycle at 150° C. According to EDS the film consisted of palladium oxide. The film grew on Si, TiN, WN, W3C and SiO2 surfaces and showed good adhesion.
Example 7
ALD of Ruthenium Oxide
Ruthenium oxide was grown from alternate pulses of bis(ethylcyclopentadienyl)ruthenium (EtCp)2Ru and water. The (EtCp)2Ru source container was heated to about 90-95° C. Evaporated (EtCp)2Ru was introduced into the reaction chamber, which was heated close to 200° C., and contacted with the substrate surface for 1.0 s. The reaction chamber was purged with inert nitrogen gas for 0.5 s to remove residual (EtCp)2Ru from the gas phase. After that, water vapor, which was evaporated from an external source bottle, was introduced into the reaction chamber and contacted for 2.0 s with the substrate surface, where H2O molecules reacted with adsorbed Ru compound molecules. Then the reaction chamber was purged with inert nitrogen gas to remove residual H2O and reaction by-products. The set of pulses was repeated until a ruthenium oxide thin film with the desired thickness was grown on the substrate. Optionally some amount of oxygen gas may be added to the H2O flow to control the oxidation state of Ru. Relatively mild oxidizing agents were used. Strong oxidizing agents, e.g. ozone, have a tendency to oxidize part of the adsorbed ruthenium into its maximum oxidation state +8 and the resulting RuO4 is highly volatile and thus the growth of RuO2 is disturbed because of desorbing RuO4.
Example 8
Reduction of Copper Oxide Using Chemical Reducing Agent
Oxidized ECD copper oxide samples covered with around 350 nm of a copper oxide layer were reduced in an ALD reactor. Several organic compounds were tested as reducing agents. Resistance of non-oxidized ECD copper samples, oxidized ECD samples and reduced ECD copper oxide samples were measured. ECD copper metal samples consisted of pure metal deposited on silicon substrate.
Nitrogen gas (N2) of a purity of 99.9999% was used as a carrier gas for the reducing agents. Tested reducing agent were MeOH (methanol), EtOH (ethanol), 2-PrOH (isopropanol), tert-BuOH (tert-butanol), PrCHO (butyraldehyde), Me2CO (acetone), HCOOH (formic acid), CH3COOH (acetic acid), and H2 (hydrogen, for a comparison).
The effect of different reducing temperatures is shown in FIG. 4, where the number after the reducing agent is the reduction temperature in degree C. Also, different reaction times were tested. The reaction time in minutes is given in parenthesis.
In FIG. 4 ECD-1 and ECD-2 stands for pure ECD copper metals without any additional treatments. O-ECD-1 and O-ECD-2 indicates samples that have a copper oxide coating (about 350 nm). The resistance values in R (ohm) measured from the samples after the reduction step are averages of 10 measurements.
Example 9
Reduction of Copper Oxide Using an Electric Current as a Reducing Agent and Integration of the Method to the Preceding and Subsequent Process Steps
FIG. 5 schematically illustrates a first cluster tool 100 in accordance with embodiments described herein. The substrate is cleaned (e.g., sputter-cleaned using nitrogen, ammonia, or argon plasma) in the first reaction chamber 110 of the cluster tool 100. The substrate is then moved to the second reaction chamber 120 of the cluster tool 100, in which a diffusion barrier layer, for example tungsten nitride carbide (WNC), is deposited by ALD on the substrate. The thickness of WNC can be selected, e.g., from the range of 1-6 nm. Then the substrate is moved to the third reaction chamber 130 of the cluster tool 100 in which copper oxide (CuO and/or Cu2O) is deposited by ALD on the diffusion barrier surface (e.g., WNC). The thickness of copper oxide can be selected, e.g., from a range of 0.6-10 nm. The first cluster tool 100 further comprises a vacuum transport module 140 and one or more load locks 150 to transfer the substrate to and from the cluster tool 100.
A barrier processing sequence is also possible in which the diffusion barrier is deposited before sputter-cleaning of the vias. The benefit of this type of processing sequence is that copper removed from the via bottom during the cleaning step cannot contaminate the via walls because the sidewalls are covered with the copper diffusion barrier as the Cu at the bottom of the via is cleaned by the directional etch.
After copper oxide deposition, a robot moves the substrate to a load lock and the substrate is exposed to clean room air. The substrate is then transported to the next processing unit, e.g., a second cluster tool 200 or an ECD tool. Use of an ECD tool is preferable because such ECD tools are typically less costly than a CVD bulk copper cluster tool.
FIG. 6 schematically illustrates a second cluster tool 200 in accordance with embodiments described herein. The copper oxide film on the substrate is reduced into copper metal with a wet electrochemical process in the first module 210 of the second cluster tool 200. The substrate is placed to a solution that contains sodium hydroxide or other water-soluble metal hydroxide. The solution is preferably kept at +50° C.-+60° C. and inert gas (e.g., nitrogen) is bubbled through the solution to remove free oxygen gas from the solution. A bias voltage of 1.4 V is applied between the substrate and the opposing electrode. As a result, deposited copper oxide on the substrate is reduced into copper metal and oxygen gas forms on the opposing electrode. In other embodiments, copper oxide is reduced into copper metal by using hydrogen plasma or alcohol, aldehyde, or carboxylic acid. The copper surface can also be exposed to an iodine compound (e.g., ethyl iodide) to activate the copper metal surface. The copper metal film is used as a seed layer for subsequent bulk copper deposition using the electroplating process to fill vias and trenches.
After rinsing the substrate to remove residual solution, the substrate is moved to the second module 220 of the second cluster tool 200. The copper seed layer is protected against re-oxidation during the transport from one module to another with an inert gas atmosphere in the vacuum transport module 230 that optionally may contain some reducing gas such as hydrogen, alcohol, or aldehyde. In the second module 220, the substrate is placed in an electroplating solution that contains a water-soluble copper compound, some acid to lower the pH of the solution, and standard additives that are commonly used to improve the quality of the growing copper film. A voltage is applied between the substrate and an opposing electrode. Copper is deposited from the solution on the seed layer, and vias and trenches become filled with copper metal. The opposing electrode consists of pure copper that dissolves to the electroplating solution during the electroplating process. After the electroplating process, the substrate is rinsed to remove residual electroplating solution. The substrate is then ready for chemical mechanical polishing (CMP). The second cluster tool 200 further comprises one or more load locks 240.
According to still another embodiment of the present invention metal oxide is first reduced with current in a bath into seed layer and then electroless plating is used for depositing metal on the seed layer. In case of electroless copper plating, the bath can for example consists of water-soluble copper compound (e.g. 12-16 g of copper sulfate/liter), reducing agent (e.g. 10-12 g of formaldehyde/liter), chelating agent (e.g. 18-21 g of ethylene diamine tetraacetic acid EDTA/liter), complexant (e.g. 10-12 g of sodium potassium tartrate/liter), stabilizer (e.g. 2-mercaptobenzothiazole) and alkali compound (e.g. 13-17 g of NaOH/liter) for raising pH. Copper oxides do not dissolve in alkaline solutions, so it is possible to use the same bath for reducing metal oxide with current and for electroless plating. Thus, only one process module is needed for bulk copper fill.
Various embodiments of the present invention have been described above. Although this invention has been described with reference to these specific embodiments, the descriptions are intended to be illustrative of the invention and are not intended to be limiting. Various modifications and applications may occur to those skilled in the art without departing from the true spirit and scope of the invention as defined in the appended claims.

## Claims

1. A method of producing a conductive thin film, comprising:
depositing a metal oxide thin film on a substrate by an atomic layer deposition (ALD) process, wherein the metal oxide thin film is selected from the group consisting of ReO2, Re2O5, ReO3, RuO2, OsO2, CoO, Co3O4, Rh2O3, RhO2, IrO2, NiO, PdO, PtO2, Cu2O, CuO, AgO, Ag2O, and Au2O3; and
at least partially reducing the metal oxide thin film by exposing the metal oxide thin film to an electric current, thereby forming a seed layer.

2. The method of claim 1, wherein the metal oxide thin film is at least 0.6 nanometers thick.

3. The method of claim 1, wherein the metal oxide thin film has a thickness between approximately 1 nanometer and approximately 20 nanometers.

4. The method of claim 1, wherein the metal oxide thin film has a thickness between approximately 1 nanometer and approximately 3 nanometers.

5. The method of claim 1, wherein depositing comprises at least three cycles of the ALD process.

6. The method of claim 1, wherein the metal oxide thin film has a resistivity less than about 500 μΩ-cm.

7. The method of claim 1, wherein the metal oxide thin film has a resistivity less than about 300 μΩ-cm.

8. The method of claim 1, wherein the metal oxide thin film has a resistivity less than about 100 μΩ-cm.

9. The method of claim 1, wherein the metal oxide thin film comprises RuO2 and has a resistivity of about 35 μΩ-cm.

10. The method of claim 1, wherein the ALD process comprises feeding into the reaction chamber and contacting the substrate with alternating vapor phase pulses of at least one first source chemical comprising a compound capable of adsorbing no more than a monolayer of metal species on the substrate and at least one second source chemical comprising a compound capable of oxidizing the metal species on the substrate into the metal oxide.

11. The method of claim 10, wherein the first source chemical is Cu(thd)2 and the second source chemical is selected from the group consisting of ozone (O3), oxygen (O2) and a mixture of O3 and O2.

12. The method of claim 10, wherein the first source chemical is copper(II)acetylacetonate and the second source chemical is selected from the group consisting of ozone (O3), oxygen (O2) and a mixture of O3 and O2.

13. The method of claim 10, wherein the first source chemical is anhydrous metal nitrate and the second source chemical is vaporized aqueous solution of NH3.

14. The method of claim 10, wherein the first source chemical is anhydrous copper nitrate (Cu(NO3)2) and the second source chemical is vaporized aqueous solution of NH3.

15. The method of claim 10, wherein the first source chemical is Co(thd)3 and the second source chemical is selected from the group consisting of ozone (O3), oxygen (O2), and a mixture of O3 and O2.

16. The method of claim 10, wherein the first source chemical is Pd(thd)3 and the second source chemical is selected from the group consisting of ozone (O3), oxygen (O2), and a mixture of O3 and O2.

17. The method of claim 10, wherein the first source chemical is bis(ethylcyclopentadienyl)ruthenium ((EtCp)2Ru) and the second source chemical is a mixture of oxygen and water gases.

18. The method of claim 1, wherein the substrate comprises a barrier film and the metal oxide thin film is deposited onto the barrier film.

19. The method of claim 18, wherein the barrier film comprises a material selected from the group consisting of TiN and WNC.

20. The method of claim 1, wherein the electric current is provided by an electrolyte solution comprising a water-soluble metal hydroxide.

21. The method of claim 20, wherein the water-soluble metal hydroxide comprises sodium hydroxide.

22. The method of claim 20, wherein the electric current is applied while bubbling inert gas through the electrolyte solution.

23. The method of claim 1, wherein the electric current is applied while the substrate is at temperatures between about 0° C. and about 100° C.

24. The method of claim 1, wherein the electric current is applied while the substrate is at temperatures between about 20° C. and about 80° C.

25. The method of claim 1, wherein the electric current is applied while the substrate is at temperatures between about 50° C. and about 60° C.

26. The method of claim 1, wherein the electric current is applied for a time period between about 1 second and about 3600 seconds.

27. The method of claim 1, wherein the electric current is applied for a time period between about 30 seconds and about 1000 seconds.

28. The method of claim 1, wherein the metal oxide thin film is exposed to the electric current in an electrochemical deposition (ECD) tool.

29. The method of claim 28, further comprising depositing metal onto the seed layer by an electrochemical deposition (ECD) process in the ECD tool.

30. The method of claim 29, further comprising repairing the seed layer prior to the ECD process.

31. The method of claim 1, further comprising depositing metal onto the seed layer by an electrochemical deposition (ECD) process.

32. The method of claim 31, further comprising repairing the seed layer prior to the ECD process.

33. The method of claim 1, wherein the reduction of the metal oxide thin film essentially converts the metal oxide into an elemental metal seed layer which has sufficient conductivity to be used for subsequent electrochemical deposition.

34. The method of claim 1, wherein the reduction of the metal oxide thin film essentially converts the metal oxide into an elemental metal to provide sufficient conductivity to be used as an electrode of a capacitor.

35. The method of claim 1, wherein the seed layer has a resistivity between about 1 μΩ-cm and about 30 μΩ-cm.

36. The method of claim 1, wherein the seed layer has a resistivity between about 1.67 μΩ-cm and about 10 μΩ-cm.

37. The method of claim 1, wherein the seed layer has a resistivity between about 1.7 μΩ-cm and about 3 μΩ-cm.

38. A method of producing a conductive thin film comprising the steps of:
A. placing a substrate in a chamber;
B. exposing the substrate to a vapor phase first reactant, wherein the first reactant adsorbs no more than a monolayer of metal species on the substrate;
C. removing excess first reactant from the chamber;
D. exposing the substrate to a second vapor phase reactant comprising a compound that is capable of oxidizing the adsorbed metal species on the substrate into metal oxide;
E. removing excess second reactant from the chamber;
F. repeating the above steps B through E at least three times to form a metal oxide film, wherein the metal oxide thin film is selected from the group consisting of ReO2, Re2O5, ReO3, RuO2, OsO2, CoO, Co3O4, Rh2O3, RhO2, IrO2, NiO, PdO, PtO2, Cu2O, CuO, AgO, Ag2O, and Au2O3; and
G. following step F, exposing the substrate to an electric current to reduce the metal oxide to metal, thereby forming a seed layer.

39. The method of claim 38, wherein in step F, steps B through E are repeated at least 10 times to form a metal oxide film.

40. A method of producing a conductive thin film comprising:
depositing a metal oxide thin film of at least 0.6 nanometers thickness on a substrate by an atomic layer deposition (ALD) process, wherein the metal oxide thin film is selected from the group consisting of ReO2, Re2O5, ReO3, RuO2, OsO2, CoO, Co3O4, Rh2O3, RhO2, IrO2, NiO, PdO, PtO2, Cu2O, CuO, AgO, Ag2O, and Au2O3; and
reducing said metal oxide thin film to a metal film on said substrate by exposing the metal oxide thin film to an electric current, thereby forming a seed layer.

41. A method of producing a conductive thin film, comprising:
depositing a metal oxide thin film on a substrate by an atomic layer deposition (ALD) process, wherein the metal oxide thin film is selected from the group consisting of ReO2, Re2O5, ReO3, RuO2, OsO2, CoO, Co3O4, Rh2O3, RhO2, IrO2, NiO, PdO, PtO2, Cu2O, CuO, AgO, Ag2O, and Au2O3; and
at least partially reducing the metal oxide thin film to elemental metal by exposing the metal oxide thin film to an electric current, thereby forming a seed layer.

42. The method of claim 41, wherein at least partially reducing the metal oxide thin film is performed in an electrochemical deposition tool.

43. A method of producing a conductive thin film, comprising:
depositing a metal oxide thin film on a substrate by an atomic layer deposition (ALD) process, wherein the metal oxide thin film is selected from the group consisting of ReO2, Re2O5, ReO3, RuO2, OsO2, CoO, Co3O4, Rh2O3, RhO2, IrO2, NiO, PdO, PtO2, Cu2O, CuO, AgO, Ag2O, and Au2O3; and
at least partially reducing the metal oxide thin film to elemental metal in an electrochemical deposition tool, thereby forming a seed layer.

44. The method of claim 43, wherein the metal oxide thin film is at least partially reduced by exposing the metal oxide thin film to an electric current.

45. The method of claim 43, wherein the metal oxide thin film is at least partially reduced by exposing the metal oxide thin film to one or more organic compounds that contain at least one functional group selected from the group consisting of —OH, —CHO, and —COOH.