TW550306B - Method for depositing layered structure on sensitive surfaces - Google Patents

Abstract

The present method provides tools for growing conformal metal nitride, metal carbide and metal thin films, and layered structures incorporating these films, from aggressive chemicals. The amount of corrosive chemical compounds, such as hydrogen halides, is reduced during the deposition of transition metal, transition metal carbide and transition metal nitride thin films on various surfaces, such as metals and oxides. Getter compounds protect surfaces sensitive to hydrogen halides and ammonium halides, such as aluminum, copper, silicon oxide and the layers being deposited, against corrosion. Layered structures (20) incorporating metal nitrides, such as titanium nitride (30) and tungsten nitride (40), and metal carbides, and methods for forming the same, are also disclosed.

Description

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 550306 A7 B7 V. Description of the invention () Field of the invention: The present invention relates to the deposition of thin films on substrates by alternate self-saturating chemistries, especially the use of A method for preventing corrosion of materials in a substrate when forming a thin film of corrosive materials. BACKGROUND OF THE INVENTION: Atomic layer deposition (ALD), commonly referred to as atomic layer epitaxy (ALE), is an advanced CVD variation. The ALD process is based on sequentially satisfying surface reactions. Examples of these processes are described in detail in U.S. Patent Nos. 4,05 8,430 and 5,711,811. The described deposition process benefits from the use of an inert carrier gas and a purge gas ta to speed up the reaction of the system. Due to the self-contained nature of the process, ALD enables near-perfect film deposition on atomic film layers. This technology was originally developed to demonstrate the uniform coating of the substrates of horizontal panel electroluminescent displays in order to demonstrate the high surface area requirements. In recent years, the application of ALD has been found in the field of integrated circuits. Its extraordinary uniformity and control capabilities enable this technology to be used in downsizing processes that are increasingly needed in today's semiconductor process development. Although the ALD process may have many applications in semiconductor manufacturing, integrating these new processes into an established manufacturing process can create many new problems. Therefore, there is still a need to improve the ALD process. The purpose and summary of the invention: Page 2 This paper is suitable for the family and the family (CNSM4 specifications (21 × 297) _y (Please read the note on the back? Matters before filling out this page)-丨 Installation ----- --Order --------. 55〇3〇6 A7 B7 V. Description of the invention (The table shows whether the refractory metal halide reacts with the steel metal (X) or does not react (0). (X) stands for lack Sufficient information to make the results of applying these reactants without inhalation. These metals are in the most likely state of oxidation. The Gibb reaction free energy is calculated using a computer program (HSC Chemistry '3.02 version, Outokumpu Research 〇 y, Pori, Finland) 〇Comparison of drawing numbers: 30 Titanium nitride 40 Tungsten nitride 50 Insulating layer 51 Barrier layer 52 Conductive element 54 Etching stop layer 56 Insulating layer 58 Grinding mask 60 Trench 62 Contact via hole (please Read the notes on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs! 50 Thin Film Invention Detailed Description: The method disclosed in the present invention can protect sensitive surfaces during ALD deposition. Those familiar with this technology people It can be appreciated that when an ultra-superimposed structure is applied, its protection against corrosion of sensitive surfaces can be applied to other structures and vice versa. Definitions To properly describe the present invention, the "ALD process" is defined as: deposition Materials are on the surface and are based on sequential and interactive self-satisfied surface reactions. The basic theory of ALD is disclosed in, for example, page 5 of the US patent

-丨 • 丨 — 丨 丨 丨 — 丨 Erding- 丨 丨-丨 丨 丨 丨-550306 A7 V. Description of the invention (Common structures usually have at least two different molecular phases. It is best to have at least three adjacent The existence of single-phase makes the mixture of molecules or atoms in space, and the difference between different parts of space cannot be found by analysis. Different phases can be attributed to the traditionally recognized differences Points, such as different crystalline junctions #, lattice parameters, crystallization stages, and the chemical composition of the thin film on either side of the phase interface. Take each phase or plating layer in the stack very thin, about It can be at 20 nm, or preferably less than about 10 nm, and most preferably 5 nm per layer. "Thin film, which means that the element or compound is separated in the true 2 gas phase or Transmission in the liquid phase from the source to the substrate. The thickness of the thin film is related to the application and may vary greatly, most from one atomic layer to 1000 nrn. The composition of the film. 'This metal thin film may contain certain metal carbides and / or metal compounds, the amount of which does not have a negative impact on the metal properties of the film, or the characteristics of ultra-fine stacking. Integration problems General halides, especially Transition metal compounds, due to their volatility and resistance to thermal decomposition, are suitable for ALD. These compounds are liquid or gas near room temperature, such as 2 titanium chloride (TiCl4) and tungsten hexafluoride (WF6). ), Etc., because it does not generate body particles in the container, so it is better. @ 了 In addition to being volatile, many of this elementary complexes allow special types of materials (such as metal-containing species) to enter the chemistry Absorption ', leaving the end of the monolayer species to be a halide, so it is cured by less than or good boronization (please read the precautions on the back before filling this page) -----— Order ----- ----% Page 7 Paper Ruler _ ^ Home Fresh (CNSM4 550306 A7

(Please read the precautions on the back before filling this page) φ-l · ----- " —Order ----------- 550306 A7

The contact via 62 can be used as a location for connecting to the underlying electrical component or wiring layer according to the circuit design. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics. Those who are familiar with this technology can use many different materials and structures for these purposes. For example, since the preferred insulating layers 50, 56 include PECVD TEOS, these plating materials may include one of a variety of other suitable dielectric materials in other configurations. For example, a dielectric material which has been developed in recent years and has a low dielectric constant (low k) as compared with a conventional oxide. These low-dielectric materials include polymer materials, porous materials, and fluorine-doped oxides. Similarly, the barrier layer 51, the etch stop layer 54 and the mask 58 may include one of the materials whose i is suitable for a given function. Furthermore, any or all of the plating layers 5 1 '54 and 5 8 may be omitted from other structures to make a double-layer mosaic structure. As shown in Fig. 7, the double-layer inlaid trench 60 and the via 62 are then lined with a thin film 150. This thin film can be selectively deposited on a special surface of the structure, but it is best to form a comprehensive and uniform deposition by ALD according to a preferred embodiment. In the illustrated embodiment, the film is conductive and allows electronic signals to flow through. Integrated circuits include interconnects made of metal. Recently, copper has become an attractive material in this field. However, copper metal can easily diffuse into surrounding materials. Diffusion effects can affect the electrical properties of the circuit and make active components ineffective. Diffusion effects can be avoided via a conductive diffusion barrier. Because ion diffusion favors the grain boundaries of thin films, non-crystalline films are believed to increase the characteristics of diffusion barrier layers. Preferred diffusion barrier materials are transition metal nitrides, such as TiNx, TaNx, and WNX. The inventors also found that metal carbides (such as WCX) are also very good conductive diffusion resistances. Page 10 This paper applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) r-- · L ---- -^-Order --------- Line · C Please read the notes on the back before filling out this page} Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 550306 Α7 Β7 5. Description of the invention () Species are not required for deposited layers, especially nitrogen atoms. Figure 8 illustrates a general three-phase cycle to deposit binary materials. However, those skilled in the art will understand that the technical principles disclosed herein can be easily applied to deposit ternary or more complex materials with ALD. Semiconductor workpieces that include sensitive surfaces are loaded into the semiconductor process chamber. An example reaction chamber, specifically designed to enhance the ALD process, is commercially available from ASM Microchemistry of Finland under the trade name Pulsar 2000TM. If required, the exposed surface of the workpiece (such as the trench and via wall sidewall surfaces and the metal bottom surface shown in Figure 6) will terminate with the first phase of the ALD process. The first phase of this preferred embodiment is susceptible to reaction with compounds ending in, for example, hydroxide (OH) or ammonia (NH3). In the examples to be discussed below, the silicon oxide and silicon nitride surfaces of the double-layer damascene structure need not be terminated separately. Some metal surfaces, such as the bottom of the via 61 (Figure 9A), can be finished with ammonia treatment. After the initial surface is finished, the first reactant pulse wave is then supplied to the workpiece if necessary. According to this preferred embodiment, the first reactant pulse wave includes a carrier gas flow and a volatile dentition material that can react with the relevant workpiece surface and further includes a material forming a partially deposited coating. In addition, the pixel-containing material is absorbed on the surface of the workpiece. In the exemplified embodiment, the first reactant is a metal halide, and the formed thin film contains a metal material ', preferably a metal nitride. This first reactant pulse wave saturates the surface of the workpiece by itself, so that any excess components of the first reactant pulse wave will not further react with the single layer formed by this process. Applicable to Chinese national standards (CNS> A4 specification (210 X 297 mm) 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 l · 丨 丨 Order --- 丨! 丨 丨-. C Please read the back first Note: Please fill in this page again.) 550306 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention () Self-saturation occurs after the single layer is finished, which can prevent further reaction of the coating. The wave is preferably provided as a gas and is therefore referred to as a halogen source gas. In some instances, the reactant material has a melting point greater than the process temperature (for example, copper chloride dissolves at 430 ° C and the process is at about 350. (implemented at time). However, for narrative purposes, if the material exhibits sufficient vapor pressure under process conditions, so that the material can be transferred to the workpiece at a sufficient concentration to saturate the exposed surface, then the function The source gas is considered to be "volatile". The first reactant is then removed 104 from the reaction chamber space. Step 104 is best to stop only the first chemically flowing gas, but still continue to flow the carrier gas for a sufficient time so that Diffusion or removal of excess reactants and reactant by-products from the reaction chamber space is preferably a purge gas that is greater than about twice the volume of the reaction chamber, and more preferably more than about three times the volume of the reaction chamber. As exemplified In the embodiment, removing 102 includes continuing to purge the gas after stopping the flow of the first reactant pulse wave for between about 0.1 seconds and 20 seconds. The removal of the intermediate pulse wave is described in the commonly-applied US patent application, 09/3 92,371, applied on September 8, 1999, and named "IMPROVED APPARATUS AND METHOD FOR GROWTH OF A THIN FILM". The disclosure will be listed as a reference. In other configurations, the reaction chambers are alternated. A complete vacuum is drawn between the chemical interactions of the compounds. For example, refer to PCT Publication No. WO 96/17107, published on June 6, 1996 under the name, METHOD AND APPARATUS FOR GROWING THIN FILMS ", The disclosure will be listed as a reference. At the same time, the adsorption effect will be applied to the Chinese standard (CNS) A4 (210 X 297 public love) on page 18 of this paper. I ------- I --β * --- --I --- ^ (Please read the notes on the back before filling out this page) 550306 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (for metal nitride layers, it is best to add In the other phase, the getter can leave one element to replace the other. Ethylboron getter is used to remove the gas atom of the complex. The example is: in the embodiment, the second reactant pulse Bo Yi writes that the two sounds of the two disciples and two chemicals need to be left behind by the single character of the getter phase. "The second reactant contains a chemical that is related to the plutonium atom. This phase of the getter is useful in other phases, such as forming a functional gas. In the example," This second reactant vein ", the skin 110 contains a hydrogen atom. The relevant nitride (eg Gu 3) source gas supplies the carrier gas to the workpiece. The 14th reactant or the nitrogen-containing material Xiao Jiao # remains previously adsorbed by a single acoustic reaction: nitrogen compounds. Specially, since the first The reactant contains gold; the halide 'first-reactant leaves no more than a single layer of metal nitride. The second reactant pulse i 10 also leaves a surface finish that limits deposition in the saturated reaction phase. Nitrogen The material with the N 为 χ tail at the end of the single layer of metal nitride and the νη3 of the pulse of the second reactant will not react. After a period of time that is sufficiently saturated and reacts with the pulse of the second reactant u 0 The material will be removed from the workpiece 1 1 2. Like removing the first reactant 104 and removing the getter material 108, this step 112 preferably includes stopping the flow of the second chemical and continuing to flow the carrier gas for a period of time in order to The pulse from the second reactant will The remaining reactants and reaction by-products diffuse out and are removed from the reaction chamber space. At the same time, in the illustrated process, the second reactant pulse wave 1 1 0 and removal 1 1 2 represent the third phase 1 1 3, And it can be regarded as the phase of nitrogen or hydrogen, because nitrogen will react with the formed film and form a part of the film, and hydrogen will be released in the reaction. Page 20 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297) %)

iMW illl --- Order --------- Line j (Please read the note on the back? Matters before filling out this page) 550306 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs In other examples, the metal source chemicals alternate with each other during each three-phase cycle, thus generating different nitrided metal layers. In the exemplified metal nitride examples (Examples 5-7) The first reactant contains metal, supplying metal to the growth layer (eg, WF6 or TiCl4); the getter contains triethylboron (teb); and the second reactant contains ammonia (Nh3) to supply nitrogen atoms to The growth layer. The examples shown on the τ plane illustrate the advantages of using halide getters in thin films> Examples. Examples 1, 2, and 4 illustrate examples of observing the corrosion of copper metal surfaces and other examples illustrate Example of the disappearance of corrosion in the preferred embodiment. The extent of corrosion has not been quantified. At the same time, the presence or absence of corrosion can be determined by optical methods and SEM images. In fact, the tolerance of corrosion will depend on the application. Source material Slaves say come Source materials (for example, metal source materials, hafnium oxides, and nitrogen atom source materials) are best selected to provide sufficient vapor pressure, substrate temperature with sufficient thermal stability, and sufficient compound reactivity to affect ALD: ,, sufficient pressure, to provide enough gas phase source chemical molecules to the substrate surface to generate a self-saturation reaction on the surface at the required rate., Sufficient thermal stability, the source chemical itself is not A simple phase of heartbeat growth is formed on the meeting surface, or harmful impurities are left on the substrate: surface during thermal decomposition. One of the purposes is to prevent uncontrolled knife from condensing on the substrate. ,, & adequate, , Will make the pulse self-saturation time to a commercially acceptable production time. Further selection criteria include the process of obtaining and processing high-purity chemicals --------- Chapter 22-page paper rule money ------ r --- IT --------- ^ (Please read the notes on the back before filling out this page) 550306 A7 B7 Employees ’Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative print 5. Inventions Explanation (The thin-film transition metal nitride layer is best obtained from a metal source material, and more preferably, it is 3, 4, 5, 6, 7, 8'mu and / or 12 of the periodic table elements with volatile or Vapor phase transition metal compounds. Basic metal thin film layers are also preferably made of these compounds or contain copper (Cu), nails (Ru) j & (Pd), silver (Ag), gold (Au), silver (Ι) 〇 made of the starting material. In a better condition, the metal and nitride metal source materials include transition metal sulfides. 1 · The halide source material first reactant preferably includes the workpiece exposed during deposition Materials with a corrosive surface, especially when combined with a second reactant. In addition, the corrosive material can help self-limit deposition due to the formation of partial distributors. Therefore, during the first pulse wave, it is forbidden to further form in the illustrated embodiment. The advantage of the rot material of the first tile should be: It provides a volatile source gas for the required deposition material. In particular, the first reactant of the preferred embodiment includes a south chemical, and a good metal is selected. As mentioned earlier, the function metal is volatile and is therefore an excellent medium to carry the metal to the workpiece. Furthermore, the end of nansin terminates the surface of the single layer of chemisorption and inhibits further reactions. This surface can thus saturate itself to promote uniform film growth. In the illustrated embodiment (see Examples 3 and 5-7 below), each of the halide source materials includes a toothed metal, which can cause etching or corrosion during the ALD reaction. For example, Examples 1, 2, and 4 all indicate that the corrosion of copper metal exposed to the ALD process includes pulses of titanium tetrachloride (TiCl4) or tungsten hexafluoride (Wf6). Page 23 This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm ---- I .--- l · ---- order --------- line j (please Read the note on the back? Matters before filling out this page) 550306 A7

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of Invention () However, as shown in Example 8, the pentafluoride (TaF5) does not etch copper metal during the deposition of hafnium nitride. Thermodynamic calculations (see Figure 5) will support this experimental result and predict that hafnium bromide and niobium fluoride will not corrode the copper metal during the deposition of nitrided metals (see Table 1). Low atomic valence functional metals have fewer available prime atoms and can therefore be expected to be less corrosive to sensitive surfaces than high atomic valence metal halides. Commercialized metal-derived chemicals can be transported as a reducing agent before the substrate space in order to reduce the atomic valence or oxidation state of the metal in the functionalized metal, thereby reducing the halide content of the functionalized metal and reducing the possibility of corrosion on the substrate surface . The use of solid or liquid reductants before substrate space is described in our review of the Finnish patent application FI 1 9992235. Therefore, metal sources such as hafnium pentafluoride, bromide and niobium fluoride are not corrosive in the ALD process in question. In addition, such a metal source material may not use the getter method disclosed below. This getter method has been successfully applied to transition metal compounds, especially selected from the IV (Ti, Zr and Hf), V (V, Nb and Ta) and VI (Cr, Mo and W) groups in the periodic table. Elemental halide. The nomenclature of these groups follows the system suggested by IUPAC. Related to specific metals, compounds formed from fluorine, chlorine, bromine, moth, and transition metals can be used. However, some dentified metal compounds such as tetrafluoride cone (ZrF4) are not sufficiently volatile for the ALD process. 2 · getter or scavenger 2 · 1 delete the compound in the example, the getter triethyl boron (TEB) can be used to protect copper metal ------------ · 1 1--1 l · —Γ ^ --------- (Please read the notes on the back before filling out this page) 550306 A7 _—____ B7 V. Description of the invention (The surface is not affected by rotten silver. For possible reaction products The following compounds have a positive effect on the absorption effect: boron halide, formed by the reaction of a halide (for example, from a metal halide, hydrogen halide or ammonium halide) and the central boron atom of the TEB molecule; Formed by the reaction of ethyl groups (for example, from a toothed metal, hydrogen or ammonium halide) and the TEB molecule; Those who are familiar with this technology will understand that the absorption effect proposed here is not limited to TEB. One type of boron compounds is boron (BxHy). At least one boron-carbon bonded volatile boron compound is not suitable Some metals are better, and hydrocarbon clusters and boron bonds are also better. In the case of too long or too large clusters and boron bonds, the central atom of this molecule may be masked, so the reaction I want to take will take too much time or may produce unacceptable process conditions, such as high substrate temperature. In addition, a getter compound is preferably selected from volatile boron compounds having at least one boron-carbon bond. 2.2 Silicon compounds Compounds such as sulphur-based clustering and crushing can be used to absorb pixels or hydrogen halides' as shown in Reaction Formula And R2. Each reaction will assume that a hydrogen halide molecule consumes one dream-carbon bond. In addition, the getter compound can be selected from volatile silicon compounds with at least one silicon-carbon bond. (CH3CH2) 4Si (g) + 4HCl (g) — SiCl4 (g) + 4CH3CH3 (g) [Rl] (CH3) 2SiH2 (g) + 2HCl (g) SiH2Cl2 (g) -f2CH4 (g) [R2] Page 25 of this Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ------------ Ac (Please read the precautions on the back before filling this page) I · --〆l · ---- Order · —I --— I — 1 ^.) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Description of the invention (Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 · 3 Germanium and Samarium Compounds

The germanium compounds are the same as the alkyl group and the ^, A, Cr, and oligomers. When the absorption of peptin or hydrogenation is required, the above two have the possibility of combining. In addition, the getter compound may be selected from volatile germanium and rhenium compounds having at least one metal-rhenium bond surface. M 2 · 4 Aluminum, Gallium, and Samarium Compounds In the case of alkylaluminum, gallium, or indium compounds, the reaction shows some harmful complexity. For example, trimethylaluminum (TMA) decomposes' when tritiated metals appear and leaves carbon atoms on the surface. The use of these compounds to absorb quotients or hydrogen hydrides will require careful arrangement of ALD process parameters. However, in poorer configurations, the getter compound may still be selected from volatile aluminum, germanium, or indium compounds with at least one metal-carbon bond. 2.5 carbon compounds In the case of carbon compounds, the bonding positions (R3 and R4) of the hydrogen halide can still be found when the molecule has double or triple bonded carbon atoms. Due to the difference between surface chemistry and gas chemistry (for absorption and absorption energy, for example), the thermodynamic calculation of the reaction is difficult. For a getter compound selected from volatile carbon compounds, the compound has at least one double or triple bond between carbon atoms. H2C = CH2 (g) + HCl (g) — H3C-CH2Cl (g) [R3] HCe CH (g) + HF (G2 H2C = CHF (g) [R4] 2.6 nitrogen compounds in the example of nitrogen compounds, Normally lS nitrogen is thermally unstable. The reaction between alkyl · nitrogen and hydrogen halide compounds is less likely to form any. Page 26 This paper is sized for China National Standard (CNS) A4 (210 x 297 cm) --- i .-- Γ--r Order --------- Line · Γ% Read the notes on the back before filling in this page} 550306 A7

V. Description of the invention () Nitrogen. However, the formation of chloroalkyl groups with alkylamines is theoretically feasible (R5). Gibb energy (△ Gf) can also be calculated at the same time. The kinetic factors affecting the response have not been resolved. For reactions between amines and hormone-related species (such as hydrogen or hydrogen or free halogens) and the formation of carbonized compounds, the getter compounds selected from volatile amines are preferably negative or close to Zero Gibb energy value. CH3NH2 (g) + HCl (g) —CH3Cl (g) + NH3 (g) Δ Gf (400 ° C) ^ 12kJ [R5] Some amines have stronger bases than ammonia (NH0. This class Amines can form acid-like hydrogen hydride molecules without damaging the bond to form a salt-like compound. This bond can enhance the removal of hydrogen hydride from the surface of steel before any corrosion occurs. It is selected from the volatile amine getter The compounds preferably form stable salts with hydrogen hydride or have a negative or near zero free Gibb energy value during the reaction between the volatile amine and the dentition hydrogen, thus forming a volatile amine-hydrogen chloride salt. 2.7 Phosphorus halides Phosphorous halides are quite stable and may use organic phosphorus compounds to absorb halogens or hydrogen hydride. The formation of metal phosphides is a competitive reaction, and related to its application, phosphorus compounds will not be accepted. Selected from the absorption of phosphorus compounds Aerosol compounds preferably have at least one phosphorus-carbon bond. 2.8 Zinc compounds Alkyl zinc compounds are commercially available. In integrated circuit processes developed today, zinc is not compatible. In the case of zinc exposure The getter compound may be selected from the group having at least one zinc-carbon bond Zinc compounds. 2 · 9 Iron and copper compounds Page 27 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ---------- (Please read the precautions on the back first (Fill in this page again) — .1 I l · --— Order ---- I--Line 1 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed organic iron and organic lead compounds to form volatile metal compounds can be selected from iron or lead with at least one metal-carbon bond ^ and gasifiers. 2 metallocene compounds. It is selected from volatile metallocene, bicyclocene, and ferrocene, the volatile derivative of metallocene, and ferrocene, all of which can form tooth metal. 2 · 1 1 Can be selected from volatile decay-fragment compounds with at least one boron-silicon bond, such as tris (trimethylsilyl) borane. Both silicon and boron ^ form volatile compounds. 2.12 Metal carbonyl compound getter The compound may be selected from volatile metal carbonyls or derivatives of volatile metal carbonyls, Such as cyclohexane difluorene tricarbonyl, in which such metals can form volatile paint metal. 2 · 1 3 General reaction formula of organic getter Halogen getter and volatile E (-CL3) mGn compound general reaction formula R6 ° E is an element in the periodic table; L is a molecule bonded to carbon C; X is a _ prime; G is an unspecified molecule or atom bonded to E; and m and η are integers, where melons The sum of n and n is related to the atomic valence of e. There is a chemical bond between E and C. E (-CL3) mGn + HX- > E (-X) (-CL3) m-iGn-i-CL3X [ R6] The general reaction formula of a hydrogen halide getter and a volatile E (-CL3) mGn compound is shown in R7. There is a chemical bond between E and C. E is an element in the periodic table; L is a molecule bonded to carbon C; X is a halogen; G is a substance such as dimethoxine, trimethyl --- i .-- ί Please read the note on the back? Please fill in this page again) Order · -4 page 28 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 550306 A7 __B7___ V. Description of the invention () and E-bonded unspecified molecules Or atom; and m and η are integers, where the sum of m and η is related to the atomic number of E. This reaction is simplified. There is actually another reaction formula between the surface and the chemisorbed E compound. E (-CL3) mGn + HX- > E (-X) (-CL3) m-iGn + CL3H [R7] getter compound E (_CL3) mGn is selected from compounds which can be bonded to halogen or hydrogen halide Or it can decompose hydrogen halide or ammonium halide to form non-corrosive volatile element compounds. 2.14 Calcination, Boron, and Compounds Related to SiHy and Bormane (BmHn), where x, y, m, and η are positive integers, and R8-R10 represent thermodynamically favorable reactions and can be combined with hydrogen halides to Less corrosive compounds.

SiH4 (g) + 4HCl (g)-> SiCl4 (g) + 4H2 (g) Δ Gf (400 ° C) =-269kJ [R8] BH3 (g) + 3HCl (g) —BC13 (g) + 3H2 (g) △ Gf (400 ° C) =-193kJ [R9] B2H6 (g) + 6HCl (g) ^ 2BC13 (g) + 6H2 (g) Δ Gf (400 ° C) =-306kJ [RIO] Ammonium halide Reacts with silane and borane (R11-R14), but they also affect the growth of transition metal nitrides due to the formation of silicon nitride or boron nitride (R15-R1 8). The reactivity of ammonium halide is mainly a well-known factor, that is, it will start to decompose into ammonia (NH3) and hydrogen halide when heated.

SiH4 (g) + 4NH4F—SiF4 (g) + 4NH3 (g) + 4H2 (g) AGf (400〇C) =-711kJ [Rll]

SiH4 (g) + 4NH4Cl—SiCl4 (g) + 4NH3 (g) + 4H2 (g) Δ Gf (400〇C) =-303kJ [R12] BH3 (g) + 3NH4F—BF3 (g) + 3NH3 (g) + 3H2 (g) Δ Gf (400 ° C) =-544kJ [R13] BH3 (g) + 3NH4Cl- > BCl3 (g) + 3NH3 (g) + 3H2 (g) Δ Gf (400〇C) =- 219kJ [R14] 4SiH4 (g) + 4NH4F- > SiF4 (g) + Si3N4 + 16H2 (g) △ Gf (400 ° C) =-1600kJ [R15] Page 29 This paper is applicable to Chinese National Standards (CNS) A4 specifications (210 χ 297 mm) ~ ------------- (Please read the precautions on the back before filling this page) 1 · --l · --factory order ---- ----- Line-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 550306 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () 4SiH4 (g) + 4NH4Cl- ^ SiCl4 (g) + Si3N4 + 16H2 (g) Δ Gf (4000) =-l 193kJ [R16] 4BH3 (g) + 3NH4F—BF3 (g) + 3BN + 12H2 (g) Δ Gf (400〇C) =-1549kJ [ R17] 4BH3 (g) + 3NH4Cl—BCl3 (g) + 3BN + 12H2 (g) △ Gf (400 ° C) =-1224kJ [R18] When there are dentified ammonium molecules on the surface of the reaction chamber (NH4F, NH4CI, NH4Br , NH4I), it is best to use silane or boron as little as possible to avoid the formation of non-volatile silicon nitride or boron nitride. When there are hydrogen molecules on the surface of the reaction chamber (HF, HC1, HBr, HI), the dosage of silane or borane can be adjusted to make the acidic hydrogen halide to form hydrogen halide or boron halide, but there is actually no remaining burnt boron. Alkane molecules can bind to the surface of the metal or metal nitride and prevent the metal or metal nitride from growing. Germane (GerHt, where r and t are positive integers) can form volatile southerly germanium, especially reacting with # H2. Although only pure silicon · hydrogen, boron-hydrogen, and germanium-hydrogen compounds are used in the example, those skilled in the art will find that similar compounds with a series of thorium in the literature can be used as this getter. In silane (SixHy), boron (β m hn) and germane (GerHt), hydrogen atoms can be replaced one by one with halogen atoms, for example, SiH4 — SiH3 and SiH 2F2 — SiHF3. Mixed halogenated europium, mouthpieces, such as SiHiFCl, can also be used. As long as at least one of these compounds—a gas atom and a fragment, boron, or staggered bond—can be used as a getter. Generally speaking, the getter compound can be selected from the group consisting of silane, borane or germanium ^ because it has at least one hydrogen atom bonded to silicon, boron or germanium.埏, 3. Source material of the second reactant The second reactant also generally includes the corrosive type of the mask exposed during the deposition, especially the surface of the second reactant. On page 30, this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm), —-1.— 一 l · —, — order --------- line (please read first Note on the back? Please fill in this page for further information.) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 550306 A7 ------ B7__ V. Description of the invention () In the example exemplified, the corrosivity of the first reactant The advantage of the species provides it with a volatile source gas to deliver the desired deposition species. In ALD, pure, metal deposition, the second reactant is replaced by other pulses of the first reactant. For example, in Example 3, both the first and first reactant pulses include WF6. Therefore, there is only one reactant taking turns in the getter phase. Each W F6 pulse may produce volatile halides or free excited-state func- tion species with decay residues such as copper, aluminum, or oxidized sensitive surfaces. For example, exposure of a metal terminated by a halide to ammonia can produce hydrofluoric acid (HF) and ammonium fluoride (NH4F). For forming binary, ternary or more complex materials, the subsequent reactants preferably include hydrogen-containing compounds, and in the example of the nitrided metal deposition example, which also provides nitrogen atoms to the nitrided metal Deposition process. The second reactant for the nitrogen atom source material is preferably volatile or gaseous. For example, ammonia gas has both volatile and south-reactive properties, and can promote the rapid reaction of chemisorbed species by the first reactant. The second reactant is preferably selected from the following clusters: • ammonia (NH3); • an ammonium salt, preferably a halide salt, especially ammonium fluoride or ammonium chloride; • hydrogen azide (HN3) and the compound Alkyl derivatives such as CH3N3. • Hydrazine (N # 4) and salts of hydrazine such as hydrazine hydrochloride; • Organic derivatives of hydrazine such as Hydrazine; • Nitrogen fluoride (NF3); • Primary, secondary and tertiary Amines such as methylamine, ethylamine, and propylamine; page 31 This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --- · I ---- L --- 『— IT- --------. Line t (Please read the precautions on the back before filling out this page) 55〇3〇6 A7 B7 V. Description of the invention () where the silicon compound represents the sensitive surface in the reaction and is toothed Hydrogen and / or ammonium halide are formed as a by-product of surface reactions. If theoretical calculations indicate that corrosion may occur, it is recommended that a getter be added to the process. This getter molecule binds aggressive molecules and prevents corrosion of sensitive surfaces. The choice of getter compounds can be based on molecular simulations. A simulation program example is HyperChem version 4.5 and is commercially available from Hypercube Inc., Florida, USA. This program can reveal the actual appearance and electrostatic potential geometry of getter molecule candidates, and predict whether molecules such as triethylboron have an accessible area to react with corrosive molecules. Molecules with physical or electrostatic shielding structures to prevent reaction with hazardous chemicals will produce undesirable getters because they increase the reaction time and productivity experienced by the reactor. Modeling reactions between molecules and surfaces requires more complex software. Cerius2 ’is commercially available from Molecular Simulation Inc. (MSI), USA and is an example program that predicts the output of chemical reactions. Chemistry To further illustrate the growth chemistry of transition metal nitride films, several examples are provided here. Generally, a practical and uniform thickness of metal nitride is required. ALD allows a single layer of metal to react with nitrogen in different pulses. In the first structure, titanium tetrachloride (TiCl4) is used as an example of a metal source material, and ammonia (NH3) is used as an example of a nitrogen-containing compound. The substrate is a silicon wafer and has an oxide layer on its surface. TiCl4 reacts with the surface containing 0H on the substrate. -OH (ads) + TiCl4 (g)-> -〇-TiCl3 (ads) + HCl (g) [R19] Page 33 This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 public love) ------------- (Please read the notes on the back before filling this page) I: --- l · --Order --------- Wisdom of the Ministry of Economy Printed by the Consumer Cooperative of the Property Bureau 550306 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy A7 B7 V. Description of the invention () Reducing agent R can be used to reduce TiCh to TiCl2. -0-TiCl3 (ads) + R (g) —-0-TiCl2 (ads) + RCl (g) [R20] The possible reaction mechanisms between nitrogen compounds and nh3 in this example are quite diverse and complex. For example: -0_TiCl3 (ads) + NH3 (g) —-0-Ti (-Cl) 2-NH2 (ads) + HCl (g) [R21] -0-Ti (-Cl) 2-NH2 (ads) — -0-Ti (-Cl) = NH (ads) + HCl (g) [R22] -0_Ti (-Cl) 2-NH2 (ads) + NH3 (g) —-〇-Ti (-Cl) (-NH2 ) 2 (ads) + HCl (g) [R23] -0-Ti (-Cl) 2-NH2 (ads) —-0-Ti (NH) NH2 (ads) + HCl (g) [R24] -0- Ti (-Cl) = NH (ads)-^-O-Ti = N (ads) + HCl (g) [R25] -0-Ti (-Cl) = NH (ads) + NH3 (g) —-0 -Ti (= NH) -NH2 (ads) + HCl (g) [R26] -0-TiCl3 (ads) + NH3 (g) ~ > -0-Ti (-Cl) = NH (ads) + 2HCl ( g) [R27] -0-TiCl3 (ads) + NH3 (g) —-O-Ti e N (ads) + 3HCl (g) [R28] Reaction formulas R2 1 to R28 are called unreduced titanium. The next TiCl4 pulse will react with the active site, such as the reaction formula 29 or 30: -0-Ti (-Cl) = NH (ads) + TiCl4 (g) —-Ti (-Cl) = N-TiCl3 (ads) + HCl (g) [R29] -0-Ti (= NH) -NH2 (ads) + TiCl4 (g) —-0-Ti (= N-TiCl3) -NH2 (ads) + HCl (g) [R30] Most nitride surface parts contain metal components for chemisorption, especially metal halides, and have = NH or -NH2 atomic groups. The surface densities of the = NH and -NH2 radicals can vary depending on the nitrogen source chemical used. When working on lower impedances, titanium with three bonds is preferred because nitrides have lower impedances than polynitrogen nitrides. In the final nitrogen crystal lattice, the bonding situation is much more complicated than the simplified structure described above. Since the paper size on page 34 applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) — — — — IL — Order · — ί Layer-— —-(Please read the notes on the back before filling out this page) 550306 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (The child occupies a different part and this Bonding has ionic or covalent bonding properties, and at the same time, possible dangling bonds or nitrogen-containing species near the crystal defect form a nitride crystal lattice. However, since the bulky ligand surrounds the active surface portion of the absorbed metal atom, a small portion , The growth rate of each cycle can be less than one molecular layer. In the second structure, tungsten hexafluoride (WF6) is used as an example of a metal source material 'and ammonia (NH3) is used as an example of a nitrogen compound rich in hydrogen atoms. This substrate is a hard wafer with a SiO2 coating. It has -OH atom groups on the surface of SiO2. In a metal pulse, three parts react with molecules (R19). Follow-up Ammonia pulses generate more hydrofluoric acid gas (R20). It is worth noting that the W-N bond is shown as a simplified form. In fact, W and N form a lattice and they distribute electrons with several adjacent atoms. -OH (ads.) + WF6 (g)-> 0-WF5 (ads.) + HF (g) [R31] -WF5 (ads.) + 2NH3 (g) —_W (5N) (=: NH ) (ads.) + 5HF (g) [R32] Due to the high capacity of hydrofluoric acid, a corrosive reaction will occur on the surface (R2 1). All reaction products are highly volatile and remain on the substrate As a result, Si02 was etched. In a nutshell, I can say that when the metal fluoride and the nitrogen compound of the gas are in contact with the oxide particles, there may be an incompatibility problem.

Si02 (s) + 4HF (g)-> SiF4 (g) + 2H20 (g) Δ Gf (400 ° C) =-43kJ [R33] In the second structure ', there is a copper metal plating layer on the surface of the substrate. Tetrachloride '(TiCU) can be used as an example of metal chloride-derived chemicals, and ammonia (NH3) is an example of hydrogen-rich nitrogen compounds. Article 351 * This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) ίihl r — r order --------- line 4 ^ · C Please read the notes on the back before filling (This page) 550306 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 丨 丨 丨 丨 ·· 丨 丨 丨 1 1 丨 丨 丨 Remuneration 丨 — 丨 I

Cu (s) + TiCl4 (g)-> CuCl4 (s) + TiCl4 (s) Δ Gf (400 ° C) =-l lkJ [R34]

Cu-0H (ads.) + TiCl4 (g) ^ Cu-0-TiCl3 (ads.) + HCl (g) -TiCl3 (ads.) + NH3 (g) — Ti (-Cl) 2 (-NH2) ( ads.) + HCl (g) As will be discussed below, regarding example 1, corrosion of the copper metal surface will be observed. 2Cu (s) + 2HCl (g) —2CuCl (s) + H2 (g) AGf (400〇C) =-41kJ [R35] 2Cu (s) + 2NH4C1 (s) —2CuCl (s) + H2 (g) + 2NH3 (g) △ Gf (400 ° C) =-59kJ [R36] Example In the implementation of this preferred embodiment, the process conditions in the space of the reaction chamber should preferably be arranged to reduce the concentration of materials produced by the gas phase reaction. The reactions between the different species are chemically adsorbed on the surface and the vapor phase skin application will saturate by itself. The reaction between the by-products and the gas getter forms a volatile chemical reactant. The deposition process can be performed under a wide range of pressure conditions, but it is best to operate under reduced pressure. The pressure in the reactor is preferably maintained between about 0.1 mbar and 50 mbar, and most preferably between about 0.1 mbar and 1 mbar. The temperature of the substrate will be kept extremely low in order to maintain the integrity of the bonds between the atoms of the thin film under the surface and to avoid thermal decomposition of the gas-phase-derived chemicals. On the other hand, the substrate temperature will be kept extremely high in order to provide a barrier to the excitation energy of surface reactions, and to avoid the natural adsorption of source materials in the reaction chamber space and reduce the concentration of gas phase reactants. In relation to the reactants, the temperature of the substrate is generally 100 ° C-700 ° C, preferably about 250 ° C-400 ° C. The temperature of the source is preferably set below the substrate temperature. Because if the source is on page 36, this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----- I Γ I l · --Γ Order --------- • line (Please read the notes on the back before filling this page) A7

550306 V. Description of the invention () When the partial pressure of the chemical vapor exceeds the concentration limit of the substrate temperature, it will jeopardize the control of growing the film layer after layer. Since the growth response is related to the self-saturating surface response, there is no need to set tight boundaries between pulse wave and clearing time. Most of the time available for the pulse wave cycle is based on economic considerations, such as the product capacity of the reactor. Very thin film layers can be formed with relatively few pulse wave cycles, and in some instances will allow the use of low vapor pressure source materials with relatively long pulse wave times. Example 1: Deposition of titanium nitride (TiN) from titanium tetrachloride (Ticu) and ammonia (NH3)-A 200mm silicon wafer covered with a PVD copper metal layer is loaded into a Puisar 2000 ALD reactor, and this reaction Commercial asm

Microchemistry Oy of Espoo, Finland. The substrate was heated to 400 ° C under a nitrogen atmosphere. The reactor pressure was adjusted to approximately 5 mbar with the aid of a mass flow controller on a nitrogen line and a vacuum pump. Next, a continuous pulse of ammonium tetrachloride and ammonia separated by an inert nitrogen gas grows a TiNx layer with Ald. A deposition cycle consists of the following steps: • Titanium tetrachloride pulse, 0.5 seconds • Nitrogen removal for 1.0 seconds • Ammonia pulse for 0.75 seconds • Nitrogen removal for 1.0 seconds This cycle will repeat 300 times to A TiNx film is formed with a thickness of about 5 nm. The growth rate of TiNx thin film is about 0.7A / cycle. The wafer is then taken out of the reactor for analysis. Four-point probe and energy dispersive spectroscopic mirror 〇 8) Measurement of production page 37 This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) I — i r I, Bu! Order — — — — — — Line · (Please read the notes on the back before filling out this page) Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 550306 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy Α7 Β7 V. Description of the invention () Generate 150 // Ω cm impedance value. Scheme R37 represents a simplified reaction. We hypothesize that a reactive moiety such as -NH and = NH on the surface can attract titanium tetrachloride molecules. After the pulse of titanium tetrachloride, -TiCl3 and = TiCl2 molecules may be generated on the surface, which can react with subsequent pulses of ammonia molecules. The theoretical result of reaction formula R37 is that a TiNx film of uniform thickness is deposited on the surface of the copper metal. However, Figure 2 shows the corrosion phenomenon on the copper metal surface. The corrosion is initiated by the reaction of hydrogen chloride (R37), a by-product of nitride formation, with copper metal. Hydrogen chloride can easily react with the remaining ammonia to form ammonium chloride (NH4C1). At the same time, ammonium chloride may also be used as a gas phase carrier for copper chloride. Example 2: A 200mm silicon wafer covered with a PVD copper metal layer was loaded with tungsten hexafluoride (WFi) and ammonia (NHy), and the substrate was heated in a nitrogen atmosphere. To 400 ° C. The pressure of the reactor was adjusted to about 5 mbar with the aid of a mass flow controller and vacuum pump on the nitrogen line. Then, a continuous pulse of tungsten hexafluoride and ammonia separated by inert nitrogen The WNX layer is grown by ALD. The deposition cycle is composed of the following steps: • Tungsten hexafluoride pulse 0.25 seconds • Nitrogen removal 1.0 seconds • Ammonia pulse 0.75 seconds • Nitrogen removal 1.0 seconds This cycle will repeat 70 times In order to form a WNX film with a thickness of about 5 nm, the qth paper size is only applicable to the Chinese National Standard (CNS) A4 specifications. □ I I --- III > I Γ I l · 11 I ^ --- ------ Line (Please read the precautions on the back before filling this page) 550306 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () The growth rate of WNX film is about 0.6A / cycle. The wafer is then removed for analysis. The etching damage to the copper metal film due to the nitride process can be seen even with an optical microscope. A large amount of hydrofluoric acid (HF) (R38) will be formed during the process. Hydrofluoric acid will attack the copper metal surface (R39). Because the vapor pressure of copper fluoride is falsely low at the temperature of the substrate, no rotten name of copper metal is generated. However, hydrofluoric acid still easily reacts with the remaining ammonia during ammonia pulses and forms ammonium fluoride. Therefore, ammonium fluoride (NH4F) can be used as a vapor phase carrier for copper fluoride (CuF), and corrosion has occurred. 2WF6 (g) + 4NH3 (g)-> 2WN + 12HF (g) + N2 (g) [R3 8]

Cu + HF (g)-> CuF + 2H2 (g) [R3 9]

Example 3: Deposition of a getter compound \ VCX A 200mm silicon wafer covered with a PVD copper metal layer was loaded into a pulse 2000TM ALD reactor. The substrate was not heated to 40 ° F in a nitrogen atmosphere. The pressure of the reactor was adjusted to about 5 mbar with the aid of a mass flow controller and vacuum pump on a nitrogen line. Then, continuous hexafluoride separated by inert nitrogen The pulse of tungsten tungsten and triethylboron (TEB) uses ALD to grow a thin layer of tungsten-rich metal. The deposition cycle consists of the following steps: • Tungsten hexafluoride for 0.25 seconds • Nitrogen removal for 1.0 second • TEB pulse 0 · 05 sec. Nitrogen removal 1.0 sec. This cycle will be repeated 70 times to form a tungsten-rich metal with a thickness of about 5nm. Page 39 This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) (Please (Read the notes on the back before filling out this page)

550306 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (Carbonide film. The growth rate of this film is about 0A / cycle. Then the wafer is taken out of the reactor for analysis. Scanning electron microscope (In the future, it will be private SEM) The results of observation did not find the corrosion of copper metal. The exact reaction mechanism between the single layer left by the gasification of the aura pulse and the Teb pulse was not known. I assume that Teb It acts as a halogen getter, leaving some carbon in the film after the formation of vaporized and fluorinated ethyl gas. Example 4: Depositing tungsten / titanium nitride (w / TiN) on copper metal covered with PVD copper A 200mm silicon wafer with a metal layer was loaded into a pulsar 2000 ALD reactor. The substrate was heated under a nitrogen atmosphere. The reactor pressure was adjusted to 5 mbar to 10 mbar with the aid of a mass flow controller on a nitrogen line and a vacuum pump. Next, a continuous wave of tungsten hexafluoride and thallium borane (B # 9) separated by inert nitrogen was used to grow a tungsten-rich thin film layer by ALD. The deposition cycle consists of the following steps: • Tungsten hexafluoride Pulse wave 1.0 seconds • Nitrogen purge for 1.0 seconds • B5H9 pulse for 3.0 seconds • Nitrogen purge for 1.0 seconds The deposition cycle will be repeated a sufficient number of times to form a tungsten-rich film with a thickness of about 5 nm. After that, continuous titanium tetrachloride and Ammonia gas to grow TiNx layer by ALD. The deposition cycle is composed of the following steps: • Titanium tetrachloride pulse 0. 05 seconds • Nitrogen removal 1 · 0 seconds The paper size is applicable to Chinese National Standard (CNS) A4 specifications (210 x 297 mm) ---------- i [l_— order --------- line · (Please read the precautions on the back before filling this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative 550306 A7 ----------- B7___ 5. Explanation of the invention () • Ammonia pulse wave 0.75 seconds • Nitrogen removal 1 · 0 seconds The deposition cycle will be repeated 200 times to form a thickness of about 5ηιη The τίΝχ film is on the ytterbium film. Finally, the wafer is taken out of the reactor for analysis. The optical microscope is used to observe the rotten phenomenon of copper metal. Therefore, it was deposited in yald

After the TiNx layer, 5nm thick tungsten metal is not enough to protect the copper metal surface from corrosion reactions. Example 5: Depositing tungsten nitride with a getter compound on copper metal A 200mm silicon wafer covered with a PVD steel metal layer was loaded into a 2 000 ALD reactor. The substrate was heated to 400 ° C under a nitrogen atmosphere. The reactor pressure was adjusted to approximately 5 mbar with the aid of a mass flow controller on a nitrogen line and a vacuum pump. Then, the continuous cavities separated by inert nitrogen were fluorinated, and the pulses of TEB and ammonia gas were grown by ALD to grow a thin film of hafnium nitride. The deposition cycle consists of the following steps: • Tungsten hexafluoride pulse 0 · 2 5 seconds • nitrogen purge 1.0 seconds • TEB pulse 0.05 seconds • nitrogen purge 1.0 seconds • ammonia pulse 0.75 seconds • nitrogen purge 1.0 seconds Repeated 70 times to form a ytterbium-rich film with a thickness of about 5 nm. The growth rate of the film is about 0.6 A / cycle. The wafer is then removed from the reactor for analysis. Page 41 This paper size applies to China National Fresh (CNS) A4 specification (21G X 297 public love) '"' ------ ---- 1 *-ί --- order ------ --- line (Please read the notes on the back before filling this page) 550306 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 —........ B7 V. Description of the invention () Observed by SEM and No corrosion of copper metal was found. The exact reaction between VIA and TEB is unknown. I assume that teb forms boron fluoride and ethyl fluoride gas and leaves negligible residues on the surface. Example 6: Depositing a tungsten nitride / tungsten titanum superfine layer with a getter compound Two different types of 200mm wafers were used in this experiment. One of the wafers is covered with a copper metal layer of PVD, and the other wafer has a copper film of electrochemical deposition (ECD). The copper-coated wafers were loaded one after the other into a Pulsar 2000tmALD reactor. The substrate was not heated to 400 ° C in a nitrogen atmosphere. The reactor pressure was adjusted to approximately 5 mbar with the aid of a mass flow controller and vacuum pump on the nitrogen line. First, a continuous wave of tungsten hexafluoride, triethyl rotten (TEB), and ammonia separated by inert nitrogen was used to grow the WNX layer by ALD. The deposition cycle consists of the following steps: • • Tungsten hexafluoride pulses • 25 seconds • Nitrogen removal 1 • 0 seconds • TEB pulses 0 • 05 seconds • Nitrogen removal 0 • 3 seconds • Ammonia pulses 0 • 7 5 seconds • Nitrogen removal for 1.0 second. TEB acts like a getter compound and removes nansine from the surface. This deposition cycle will be repeated 70 times to form a WNx layer about 5 nm thick. The growth rate of WNX is about 0 6A / cycle. Next, the continuous veins of titanium tetrachloride and ammonia separated by inert nitrogen page 42 This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) — I— III -1 Γ l ~ l ·-, —Order-— —! — Line (Please read the notes on the back before filling this page) 550306 A7 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (Wave ALD grows on the WNx layer. The deposition cycle is determined by the following steps Composition: • Titanium tetrachloride pulse 0 · 05 seconds • Nitrogen removal 1 · 0 seconds • Ammonia pulse 0.7 5 seconds • Nitrogen removal 1 · 0 seconds This cycle will repeat 300 times to form a TiNx film with a thickness of about 5nm. On WNX film. The growth rate of ΤΝχ film is about 017A / cycle. Then the wafer is taken out of the reactor for analysis. Four-point probe and energy dispersive spectroscope (EDS) measurement give about i40v Ω crn. Resistivity. The same deposition procedure is used for both forms of copper metallized silicon. Figures 3 and 4 show that no pitting or corrosion occurred on the copper metal during deposition. In addition, 5nm thick WNX was deposited during TiNx deposition. It is enough to protect the bottom PVD or ECD copper metal from corrosion. Example 7: Depositing titanium nitride with a getter compound on copper metal-200inm silicon wafer covered with PVD copper metal layer is loaded into Pulsar 200 0 ALD reactor The substrate was heated to 400 ° C under a nitrogen atmosphere. The pressure of the reactor was adjusted to about 5 mbar with the aid of a mass flow controller and vacuum pump on a nitrogen line. Next, continuous titanium tetrachloride separated by inert nitrogen The pulses of TE, TEB and ammonia gas grow titanium nitride layer by ALD. The deposition cycle consists of the following steps ... • Four gasification titanium pulses 0. 05 seconds • Nitrogen removal 1 0 seconds • ΤΕΒ pulse 0.05 Second page 43 This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) IIILI-I Γ I l · I ΙΓ ^ --------- (Please read the precautions on the back first (Fill in this page again) 55〇3〇6 A7 B7 5. The invention description printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (• nitrogen removal 1.0 sec. • ammonia pulse 0.75 sec. • nitrogen removal 1.0 sec. This cycle will be repeated 300 times to form a TiNx film with a thickness of about 5nm. The growth rate of the T i NX film is about 0 · 17 A / cycle. Then the wafer is taken out from the reactor for inspection. When the magnification is 40 times The phenomenon of rotten name was not observed when observed with an optical microscope. It does include surface reactions. The characteristics are not known. Without being bound by theory, I believe that titanium tetrachloride molecules are best attached to the = NH and -NH2 groups on the surface. Some reactions that release hydrogen chloride are shown in (R 2 8) and ( R 2 9). We assume that TEB can remove the released hydrogen chloride. = NH (ads.) + TiCl4 (g) — = N-TiCl3 (ads.) + HCl (g) [R4〇] _NH2 (ads.) + TiCl4 (g) —N (_H) (-TiCl3) (ads.) + HCl (g) [R41] A further process improvement is to follow the pulse of ammonia and increase the pulse of TEB to absorb the remaining hydrogen chloride formed in the surface reaction molecule. Some reactions that may release hydrogen chloride are shown in Reaction Formulas R42 and R43. -TiCl3 (ads.) + NH3 (g) — TiN (ads.) + 3HCl (g) [R42] = TiCl2 (ads.) + 2NH3 (g)-> = Ti (-NH2) 2 (ads.) + 2HCl (g) [R43] Example 8: Deposition of tantalum nitride

A copper-coated silicon wafer with a size of 50mm X 50mm was loaded into an F · 120TM ALD reactor, which was commercially available from ASM Microchemistry, Oy of Espoo, Finland. The substrate was heated to 400 ° C in a nitrogen atmosphere. The reactor pressure was adjusted to approximately 5 mbar with the aid of a mass flow controller on a nitrogen line and a vacuum pump. Next, the paper size of the inert forest page applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ________ 'Ik (Please read the note on the back? Matters before filling out this page) I Γ —-l ·- -Order --------- line- 550306 A7 B7 V. Description of the invention () The details disclosed, people familiar with this technology can also use it to implement other embodiments. In addition, the present invention is not limited to this preferred embodiment, and the limitations of the present invention will be defined by the following patent application scope. — — — — — — — — — I l · I l · III ------ I-- (Please read the precautions on the back before filling out this page) Printed on paper Applicable to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

55030 疔 702? Pifl is a "state H, g gentleman machine repairman 'application for patent scope A8 B8 C8 D8 ~ supplement c / in the method of conductive laminated structure on the substrate in the reaction space contains at least two The layer is adjacent to the thin film layer, and the method includes 10,000 methods to save the mouth ... — make a first * resident compound ~~ JTiLteLIj = 1 The thin film layer is bad, and the composition of the parent thin film layer and the adjacent thin film layer is different. 2. The method as described in item 1 of the scope of patent application, wherein the "_________ composite structure includes at least three layers. • The method described in item 2 of the scope of patent application, where each layer and the adjacent film layer have different compositions (please read the precautions on the back before filling this page) 4 · If the scope of patent application is the first! The method described in item 1, wherein the metal compound thin film layer includes a metal carbide. • The method described in item 1 of the scope of patent application, wherein the metal compound thin film layer includes a metal nitride. -Order --- Printed by Shellfish Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economics 6. The method described in item 1 of the scope of patent application, wherein at least one thin film layer contains a metal element. The method described above, where the combined structure is the diffusion barrier layer β in the integrated circuit. • The method described in item 1 of the scope of the patent application, where «this paper size applies to a national standard (CNS) A4 specification (210 X 297) (Public love) 550306 A8B8C3D8 Consumption cooperation between employees of the Intellectual Property Bureau of the Ministry of Economic Affairs. F ± printed t, the scope of the patent application and the structure are formed on the substrate that is easily eroded by noodles. Method, in which the _ALD type process includes providing reactants with different pulse waves in multiple deposition cycles, each cycle including at least: providing a first reactant and chemically adsorbing no more than about a single layer of function The compound end material is on the surface; the excess first reactant located in the reaction chamber space is removed; and the fusible compound is absorbed from the single layer before the cycle is repeated. The method described above, wherein each cycle further comprises supplying a second reactant related to hydrogen. 1 1. The method according to item 10 of the patent application scope, wherein the second reactant related to hydrogen comprises a nitrogen source. 12. The method according to item Π of the scope of patent application, wherein _ source of the atmosphere-contains gas. 1 3. The method according to item 11 of the scope of patent application, wherein the first reactant includes a side metal ~ 14. The method as described in item 9 of the scope of patent application, where _ the surface contains copper metal. The paper size of the 50th ear applies the Chinese National Standard (CNS) A4 (210 X 297 mm) --- r. ----- ^ --------- (Please read the notes on the back before filling in this page) 550306 A8B8C8D8 t, patent application scope 1 5. The method described in item 14 of the patent application scope 'Where_surface (please note the back of Mti before filling this page) Contains the type of silicon oxide. 16. The method described in item 9 of the scope of the patent application, wherein the surface is formed on the copper metal with a material less than 5 nm thick. Ί 7. The method described in item 9 of the scope of patent application __ The surface contains metal 〃 1 8. The method as described in item 9 of the scope of patent application, wherein _ [and 包含 include reduction. 19. The method as described in item 18 of the scope of patent application, where _ absorption Contains material that exposes the end of the compound in the compound. 20. The method as described in item 18 of the scope of the patent application, wherein the compound-contains triethylboron (TEB). 21. The method according to item 1 of the scope of patent application, wherein the superimposed structure is a conductive diffusion barrier layer ^ '2 2.-A day-to-day structure, which includes at least three thin-film plating layers, each of which has a thickness less than ^ _f The thickness of Onm, at least one layer is selected from the page containing page 51. The paper size is applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 cm) 550306 A8B8SD8 Printed by the Shellfish Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Patents cover clusters of metal and metal nitride. 23. The laminated structure described in item 22 of the patent application, wherein each thin film layer has a thickness of less than 5nm. 24. The laminated structure described in item 23 of the patent application, which includes 4 to 250 layers of film Floor. 25. The superimposed structure according to item 24 of the scope of patent application, comprising a film layer of 4JJ_201. 2 6. The superimposed structure according to item 24 of the scope of the patent application, wherein the berry-plating layer includes a metal compound different from the adjacent plating layer. 2 7. The superposed structure described in item 26 of the patent application, wherein each plating layer contains a composition different from that of the adjacent plating. 28. The superposed structure described in item 27 of the patent application, wherein two different nitrogens The metallization layers are alternately formed. 2 9. The day-to-day structure as described in item 26 of the scope of patent application, which includes' at least one metal layer 0 yfszir 111 I! I · IJ11111 ^ 0 — 111111 (please note on the back of wti before filling out this page) The standard of this paper is applicable to Θ National Standard (CNS) A4 specification (210 X 297 mm) 550306 A8B8C8D8 Conjugation knot i, among which the scope of application for patent is 30. It includes at least one metal carbide as described in item 26 of the scope of patent application Floor. 31. A method of depositing material on a substrate in a reaction chamber space. The substrate includes a surface that is susceptible to attack by self-chemicals. The method includes at least providing pulses of reactants in multiple deposition cycles, each The cycle includes at least: providing the first reactant and chemically adsorbing no more than about a single layer of the end compound species on the surface; removing excess first reactant and reaction byproducts located in the reaction chamber space; and Absorb the fuction from the single layer before repeating the cycle. 32. The method as described in item 31 of the patent application scope, wherein the first reactant comprises a fuming metal. 33. The method according to item 31 of the scope of patent application, further comprising providing a second reactant and reacting with the material type after absorbing the fusible compound. 34. The method of claim 33, wherein the second reactant comprises a nitrogen source and the material comprises a transition metal vapor. 35. The method described in item 31 of the scope of patent application, which further includes supplying a source of iron and reacting with the type of the material and the material contains transition metal carbon No. 537Γ This paper standard applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) (Qi first read the precautions on the back and then fill out this page) --- Γ .1 I--I --- I ---- 550306 A8B8C8D8 Patent Application Compound; 6. The method according to item 1, wherein the film is contained in a stacked stack. Materials ------------.—.----- Order -------- (Please fill in this page with the notes on the back first) Paper size of ear 54 Applicable to China National Standard (CNS) A4 (210 X 297 mm)