TWI254752B - Full-scale electrochemical electroless-plated deposition process of silicon-based dielectric insulated material - Google Patents

Abstract

The present invention relates to a full-scale electrochemical electroless-plated deposition process of silicon-based dielectric insulated material, which is a novel method to develop a process (sensitization/activation) other than conventional electroless palladium seed crystal so as to perform electroless-plated thin film deposition on the amphiphilic silicon-based dielectric insulated material. After modifying the surface of the silicon-based dielectric material (silicon dioxide or silicate glass), sequentially using chemical solution to perform full-scale electrochemical deposition treatment; however, for hydrophobic silicon-based dielectric material (polysiloxane), the process should be adjusted by performing selective plasma surface treatment and/or soaking in highly oxidative basic solution so as to finish the pattern-creating process of the self-aligned electroless-plated metallic thin film by the use of the full-scale electrochemical process.

Description

1254752 Nine, invention description: [Technical field of invention] H Ming system is about the whole process of a bismuth-based dielectric insulation material 7 / 1 1 plating 'child process, especially one for the micro-electric ^ half The cerium oxide dielectric insulating material of the V-body industry, 矽=glass material, fiber-optic cerium oxide cerium material and the stone-like octagonal surface of the genus catalyzed metal nanoparticle and electroless plating, Special film/redundancy, especially the development of hydrophobic insulating materials, the glow discharge plasma treatment technology to facilitate the metal production in solution, and the subsequent use of fully electrochemical (electroless plating) sinking metal film . These catalytic particles contain Ni, Co, Fe, g Cu, and the electroless metal film contains Ni, c〇, Cu, Ni_p, c^Pa^Ni.W(B)^, which is sensitized by conventional SllCl2 and PdCl2. /activated seed catalysis::: Λ one does not need to consume expensive Pd and consumes low melting point τ, d can provide substrate surface coverage protection, through hole clock: ugh-h〇le) deposition, fiber surface metal seal coating Overlay, even self-alignment "patterning," the functional technology. [Prior Art] Luo Baguang Electronics / Optoelectronics semiconductor industry uses a variety of surface coating, Xiji (or carbon-based) dielectric insulation materials, such as Polycrystalline printed circuit board material, and the main component of the printed circuit board's main line of 'the surface must be sealed with a layer of minerals to prevent = main: dye intrusion (by physical vapor or chemical vapor deposition "king Mainly, Shixi wafers have also been able to replace the earlier discovered errors by using the thermal oxidation method to grow 1254752 dioxide. (G〇 semiconductor materials' and become the most widely used semiconductor substrate material; Undoped Silicate Giass (USG) The most commonly used shallow trench insulation (.L Trench Is〇lation) material for integrated circuits (MOS devices) and Phosphosilicate (PSG) and borophosphonate glass (B〇r〇Ph〇Sph) 〇 silicate, BPSG) is also a metal pre-dielectric material commonly used for Ic components. (Premetal DieleetHes }: yttria and lanthanum low dielectric constant dielectric materials are also commonly used to isolate copper (or aluminum alloy) components. The main conductor. A metallic diffusion barrier layer must be deposited between these dielectric layers and the metal conductor to prevent mutual mixing or compounding reaction. Electrochemical (electroless plating and electroplating) deposition of a Co-based or Ni-based film is quite potential. Barrier layer material. However, all of the above insulating dielectric materials cannot catalyze the growth of electroless metal film. Although some methods, such as: one-stage activation of strontium seed growth, replacement (or impregnation) deposition (by (8) (10) Plating ), polymer grafting (Grafting) and photo-degradation of metalorganisms, have been tried to replace the Sensitization/Activation process to grow seed crystals (particles), 3], but helium, the sensitization/activation process is still a commonly used method for growing catalytic particles. This process involves first performing a two-stage or one-stage crystal on the dielectric substrate after acid (surface roughening) treatment. The growth process of the two-stage process is as follows: the substrate is sensitized with SnCl2/HC1 acid solution to generate stannous (Sn2+)-dispersed ions on the surface, and then activated by PdCh/HCl acid solution: Pd2+ will be Sn2 + Revert to Pd neutral particles. In addition, one-stage activation involves directly immersing the substrate in a SnCh/PdCh mixed acid solution to form a sn-Pd composite particle, 1254752, and further undergoing an Acceleration treatment to remove Sn2+ coated on the periphery of the particle. Therefore, this process is quite cumbersome. Another disadvantage of this process is that the Pd particles are relatively prone to agglomeration and form particles having a size greater than 100-200 nrn, and thus generally cannot be used to grow an electroless metal film having a thickness of S 1 Onm. Therefore, the development of a new seed crystal process that is different from sensitization/activation has become the goal of the industry's most active efforts. As can be seen from the above, there are still many shortcomings and deficiencies in the above-mentioned conventional techniques, which are not a good design and need to be improved. In view of the shortcomings and shortcomings derived from the above-mentioned conventional process technology, the inventors of the present invention have improved and innovated after the trial, and after years of painstaking research, finally successfully developed the entire electrochemical electroless plating deposition of the (IV)-based dielectric insulating material. Process. 【Contents】 袓+入<!%丞 dielectric insulating material Wangcheng electrochemical electroless deposit process, combined with Lai 2 mixing process: H;, 02 single vacuum glow discharge plasma surface modification length dimension only , on the surface of the "electrically insulating substrate: ultra-fine catalytic particles of only 2-4" (c〇, hundreds (or thousands) _ / Nl t Γ, up to 2 °, as large as electroplated film The N2/H2 “environmental atmosphere” of the metal, which is not a metal-based air pollution, such as 3 persons/amp; or Fe, does not have a matchability (currently, the fluorine-containing gas: the sub-remark process has a good Engrave the atmosphere, but it will endanger the environment, security and security;: 'Commonly used dry or money to cover the system can not only be a large = people.' [5]. Read the entire process of electro-chemical production, exempt Pdci2, public c / 丨 layer / The use of metal laminated film 2, and can deposit 1254752 as a metal film of 2 〇nm, and has a self-contained J J product, far from the traditional sensitization / activation comparable. 可. Can achieve the above objectives The bismuth-based dielectric insulating material, the electrochemical electroless mineral deposition process, is developed differently from the traditional non-electricity: seed crystal process (sensitization / live a novel seed growth method, =, 'ba is a hydrophilic and hydrophobic two (four) based dielectric insulating material for 2 plating (E) eCtr〇 ess-pIated) film deposition. After the surface modification of cerium oxide and bismuth silicate glass, the electrochemical deposition process is carried out according to the chemical solution: (1) immersion immersion (to produce Si-〇-negative potential surface), (2) metal salt; (I, with metal ion particles), (3) Reductive solution impregnation = high temperature treatment in the original hydrogen atmosphere (to reduce metal ions to neutral gold 2 particles), (4) non-electrical film deposition. Because of this process The adsorbed electroless catalytic metal particles do not agglomerate and have a size of only 2-4 nm, so they can be used to grow an electroless thin film having a thickness of only "plus or / as large as several hundred" and thousands of nm. For hydrophobic germanium-based dielectric materials (oxygenated alkane polymers), this process must be slightly modified: (1) using appropriate K/H2 or 〇2, 仏, and plasma treatment to remove surface hydrophobic groups, It can produce wetting behavior for the adsorption/reduction of metal ions. (2) Using high oxidation The alkaline solution can produce the surface of 〇h termination (Si-Ο-Η), and dehydrogenate in sequence to transform into a §丨_〇_ negative potential surface, thus adsorbing metal ion nanoparticles. The slurry surface treatment and/or the high oxidizing alkali type solution impregnation can be used to complete the self-aligned electroless metal film pattern by using this full-process electrochemical process. [Embodiment] Please refer to Figure 1. The basic flow diagram of the film deposition of the present invention, as shown in the figure, the steps of the plasma modification treatment and the colloidal chemical deposition of the present invention: Step 1: Mixing (N2/H2) or single-(2, H plasma surface Modification treatment (removal of hydrophobic base unit); electric sinter dielectric insulating (poly) material surface cracking - two suspension, one s) and high activity [two into two steps for "hydrophobic dielectric substrate "It is especially important to carry out the adsorption of the catalyzed particle in the subsequent step; the shape of the droplet I can be described in Fig. 2" to illustrate the dielectric polymerization of the second unit of the plasma surface (called Si-Η). Material; materials that are not treated with plasma have poor wettability, so The contact angle with a droplet shape (Drop-Shape) measured by the near 96. Therefore, the hydrated metal particles cannot be smoothly adsorbed, and after proper plasma treatment, the surface wettability is greatly improved, so that the droplets can be nearly laid on the surface (contact Shaw 24.), and the smoothness can be achieved. Causing the adsorption of hydrated metal particles; ^ Step 2: Alkaline solution impregnation (negative potential treatment on the surface of the dielectric layer), the alkaline aqueous solution with appropriate pH is used to impregnate the ruthenium-based dielectric substrate; the active surface will adsorb a large amount The hydrogen (oxygen) group, as shown in (2a), immediately produces a dehydrogenation reaction. The so-called dehydrogenation reaction is to remove the surface of the metal oxide having the OH "terminated" group into a suitable acid-base environment, and remove the hydrogen ions in the 〇H group by an acid-base equilibrium reaction. And forming a surface region with a negative potential. For example, when Si〇2 is immersed in a solution having a pH greater than its Isotal Point (IEP), the following dehydrogenation reaction is carried out: -SiOH^fi + OH '^ -Si0^s~+H9〇 or -SiOH surface->-Si〇 surface-+H4" The above-mentioned dehydrogenation reaction can oxidize 1254752 (such as Si〇2) in the metal containing 〇H group. A surface with a negative potential (Si 〇 _) is formed. The dielectric substrate after dehydrogenation will be as shown in Figure 1 (2b) [5]; 7 Step 3: Metal salt solution immersion (negative potential) Surface-adsorbed metal male granules are treated with granules; after a dielectric substrate having a surface negative potential is impregnated with a solution of other metal-based salts such as a Co- or N1-based solution, gold f-ion coulomb electrostatic adsorption is generated (or The behavior of ion exchange 'the atomic number of the episode distribution due to the particle surface θ 'class metal ion nanoparticle' Metal ion reduction treatment (formation of neutral metal seed crystal micro, quotient ~ / original 敎 atmosphere (four) original chemical solution on the substrate into the original;! · Health:: later 'the cationic particles adsorbed on the surface can be returned' , ''', belongs to the particle, has the function of catalytic electroless plating; liquid, (4) in the absence of electricity, the substrate is successfully processed in the substrate c, Ni, Cu, etc. gold tc-ot gold (C〇-P, Ni-P···etc.), or ternary W_P, Ni_w-P··., etc.) deposition of thin films. Point, = conventional sensitization / activation growth of seed particles - this lack of the invention is fully utilized Electrochemical method production; lack of % security, manufacturing to another two. In addition, the monk * / tongue-free non-electric mines made "丄,: t plasma physics and colloidal chemistry, this patent case also issued three, For the self = ^ selective gold & integration process; please refer to the diagram intention, by the < remote selective electroless metal film deposition process mouth + from the figure, the process steps are: metal it summer hydrophobic substrate (or film) masking treatment; using a mask; Hard Mask) or photoresist pattern process to create a mask activation process; Step treatment to remove the surface hydrophobic base unit; 1254752 Step 3: Mask removal; remove the hard mask 留. Leave the pattern of "hydrophilic, area; - fly first resistance, residual step four: self-alignment metal film deposition Use Figure 1:::: to step 5 to carry out nano-catalytic particles and electroless plating: In addition, after step 2, 'directly carry out the self-alignment film, and then remove the mask. A comparison illustrates the difference between the present invention and the sensitization/activation method. ^The difference between the present invention (ultrafine microcatalytic seed crystal) and the sensitization/activation method

Seed layer technology Remarks Plating composition Operating cost Plating stability Bad insurance Public security Seed characteristics Self-alignment Plating thickness

---------—— Catalytic seed sensitization/activation of seed metal base salts PdCl2/SnCl2 Low high * +pd expensive high and low high f * low "HC1 and HF corrosive 2-5nm &gt ; lOOnm* % easy to polymerize * no 'pro/hydrophobic difference $ 20nm > lOOnm

Before the best embodiment, the invention will be based on the introduction of Table 2, the conditions of the water treatment, the selection of the electrochemical solution, and the process of the process, the plasma treatment conditions, the electrochemical solution formulation and the classification.

Alkaline solution T, t Ni(N〇3)2/Co(N〇3)2 ------ T f_ 25-80〇C, 10 minutes 25°C, 10 minutes 11 1254752

n m. ^ 7 milk: ^ yuan) w electrical material is important. The plasma atmosphere can be selected from Ν2/Η^^Ν2, H”.

body. Among them, 〇2 plasma has the strongest removal rate of hydrophobic base unit, but the input energy is too high, which will cause the destruction of the main 矽7-like Si-O of the siloxane polymer; ^ Hydrophobic group without harming the polymer main structure, where N2/H" is better than N2, and a single atmosphere [4, 5]. VIII 2 2 Effect Alkaline solution formulation and metal ion adsorption Depending on the surface of the substrate, an appropriate alkaline solution (containing composition, type, concentration, temperature) must be used to produce an effective surface treatment. The successful production of metal ion adsorption is the L surface activation step.

Metal Ion Reduction Treatment In addition to the high temperature hydrogen reduction heat treatment which is commonly used in humans, the present invention also creates a chemical solution reduction treatment technique. The following is a description of the invention using two representative ruthenium-based dielectric materials, ruthenium dioxide and ruthenium oxide. The following is a combination of synchrotron radiation absorption, transmission electron microscopy (TEM) and atomic force microscopy (AFM) and scanning electron microscopy (SEM) to illustrate the adsorption, reduction and electroless deposition of metal ion particles. Finally, an example is given to illustrate the patterning process of self-alignment. Please read Figure 4, Synchrotron Radiation B 2 and L3 (845-875eV) "12 1254752 Structure" absorption spectroscopy confirmed the dioxotomy (with the money-burned polymer enamel substrate through the graph - process 'has already adsorbed metallic particles ( The fact that Ni is electroless (co). The spectrum (a) is the original base W, the peak of the metal signal is not obvious (825eV weak peak '·', the background contribution of the analytical instrument); the test piece 2 after the ion adsorption Now, the signal 'and after the reduction of the metal ion particles 4 1 , this peak will turn into the peak of the neutral metal Ni, as shown in the provinces (b) and (c) [7]. This transformation shows that the Ni2+ particles have indeed It is made of neutral Ni particles. These particles can be used as a Π〇 (or...)-, binary or ternary alloy film: the illustration in Figure 4 is the signal of the electroless c〇 film. ^Nothing The TEM dark field pattern of the treated ruthenium dioxide dielectric substrate is a fuzzy feature and a scattered electron diffraction pattern, as shown in Fig. 5 (a); but after the metal ion adsorption/reduction treatment, D (10) months Dark field image and electron diffraction pattern confirmed that ultra-fine (2-4_) Ni crystal particles of high-density I have been "Implanted, 'dielectric materials, as shown in Figure 5(b); they can be used as electroless plating catalysts and promote thin metal films as small as 20 nm (up to hundreds, thousands of nm) Formed, as shown in Figure 5 (C). Figure 6 is an SEM cross-section example of electroless Co deposition on the surface of 〇2 for 10 minutes, the thickness of the electroless c〇 film is about l〇〇nm. In order to correspond to the three-dimensional space AFM shadow I of the sample piece of Fig. 5, (a) in Fig. 7 shows that the surface of the substrate which is not subjected to metal ion particle adsorption has almost no obvious features' and its average thickness (I) is 〇. 65. This result is consistent with the TEM image, as shown in Figure 5 (4). After the s+ adsorption, the Ra rises slightly to μ-. After the reduction treatment, the surface of the dielectric layer is clearly similar to the analysis of the ferrets. The presence of ultrafine Ni particles of 1254752, Ra rose to 24 nm. These densely distributed ruthenium catalyzed particles can be used to deposit electroless plating films. After deposition for a few minutes, it can be seen that c is still uncombined. Up to 81 faces); c〇 deposited at 2 minutes has been combined into a nearly continuous film, so its Ra is reduced to 3.69nm, as shown in Figure 7 (〇AFM and & Figure 5) TEM image. Since the size of Ni catalyzed particles is only 2_4_ and there is no agglomeration phenomenon, it can catalyze growth thickness of only 2 Co film on the surface.

The hydrophilic Si〇2 dielectric material does not have to be subjected to any electrical surface treatment and is immersed in a general-purpose test solution to generate a negative potential. However, the 'hydrophobic money base phase must first be treated with a plasma to form a hydrophilic surface, and an alkaline solution containing a strong oxidizing agent must be used to produce the surface of the OH-tenninated terminal, and sequentially Hydrogen is & 〇_ (negative potential surface). After impregnating the hydrophobic ascites substrate with a suitable strong oxidant and a "selective" plasma surface treatment or oxidative test solution, the process of Figure 3 can be used to sequentially generate the sites, Plating metal (eg · & p ^ π

The case is shown in Figure 8. .C. Picture of the film with ... "Previous technical introduction

The above is a detailed description of the possible embodiments of the present invention. The present invention is not intended to limit the scope of the present invention. The scope of the broad I I basic theory of the invention

* From / g VII, I Ming content and "Invention Example 筇卞" Only he said, "The present invention and hydrophobic di-type ruthenium-based dielectric material", plasma surface modification disk + electrochemical process Depositing electroless metal thin ye - ^ ig , . ^ Shounian is the first creator of the page, Ren is indeed innovative in the technical mind, U is better than the traditional sensitization / 14 1254752, process, and can use the above metal Thin commonly used bismuth dioxide and bismuth citrate; The electronic/photovoltaic industry's materials are used to enhance the surface protection, purification and diffusion barriers::, / a variety of functions, and can be self-aligned choice = two = passivation should be "discriminatory and progressive legal : 提出 Apply in accordance with the law, and ask the f bureau to approve the application for this invention patent.

15 1254752 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the basic flow of film deposition according to the present invention; steps (1) to (5) and particle/adsorption theory; Fig. 2 is a schematic diagram of droplet shape experiment; illustrating lubrication of hydrophobic dielectric material Poority (a), but after the appropriate plasma surface modification, its lubricity is greatly improved, so the contact angle drops rapidly C b ); Figure 3 is a self-aligned selective electroless metal film deposition flow diagram; Step (1) masking the unreacted surface with a mask on the surface of the hydrophobic material; step (2) treating the unmasked portion with N2, H2, 02 or N2/H2 plasma; step (3) removing the mask, plasma The surface treatment site forms a hydrophilic region; step (4) performs a full-process electrochemical self-alignment selective deposition process; Figure 4 shows the original dielectric material (a) through the process of Figure 1; Ni ions adsorption (b), adsorption ions Reduction treatment (c), high-resolution X-ray absorption energy spectrum with electroless Co deposition for 1 minute (inset); Figure 5 is the original dielectric material (a) after Ni2-ion adsorption/reduction treatment (b) , with electroless Co The penetrating electron microscope bright field image and the selected area diffraction pattern exhibited by deposition for 2 minutes (c); Figure 6 is a non-electrical Co metal thin film test piece for performing the i 〇 minute deposition on the ceria substrate using the flow of Fig. 1 Scanning electron micrographs; Figure 7 shows the original dielectric material (a) sequentially subjected to Ni2+ reduction (b), electroless Co deposition for 1 minute (^) and 2 minutes (d) atomic force microscopy; 16 1254752 The 矽 dielectric layer/Co-WP/Cu "metal half" (MOS) capacitor structure is selectively fabricated using the "self-alignment" process of the electrochemical integrated deposition process of the present invention. [Main component symbol description] 17

Claims (1)

1254752, the patent application scope is a full-process electrochemical electroless plating deposition process of a ruthenium-based dielectric insulating material, the electro-hydraulic surface modification of the ten-based dielectric substrate and the film material of hydrophilic and hydrophobic type, and the whole process electroless electroless plating The metal deposition process, combined with the theory of electro-hydraulics and colloidal chemistry, is sequentially prepared by the following steps: Step 1··The surface of the plasma is modified; v1. The test solution is impregnated (or dehydrogenated); Step 3: Metal salt liquid immersion # (metal ion particle surface adsorption); 乂Step 4. Metal ion particle reduction treatment; V step 5. Electroless plating film deposition, and deposition of micro-electricity metal film on the surface of the ruthenium-based dielectric material. 2. 3. I. I declare a full-scale private electroless electroless deposition process for the ruthenium-based dielectric insulating material described in the first paragraph of the patent scope, wherein the plasma treatment can be used for cerium oxide insulating material, bismuth silicate glass, and optical fiber. The bare-line cerium oxide substrate and the cerium-based dielectric material such as helium oxygen and k σ material generate an active surface, so that after the alkali solution, the negative electrode potential surface is generated to adsorb any ultrafine metal ion having catalytic electroless plating. particle. The invention discloses a full-process electrochemical electroless plating deposition process of the bismuth-based dielectric insulating material described in the second paragraph of the patent scope, wherein the cerium oxide insulating material, the cerium salt broken glass, the cerium oxide-based optical fiber bare wire material and the like are hydrophilic. The electroless electroless metallization film deposition process of the ruthenium-based dielectric material can be performed on the electroless thin film of the type of dielectric loose material by using _ 18 18 1254752 :... 孜 孜 'I can be treated with or without electricity treatment. ' (In the whole process electrochemical electroless plating deposition process of Shi Xiji dielectric insulation material mentioned in the second paragraph of the patent scope, the whole process electrochemical electroless plating thin film deposition process of the hydrophobic polymer material of the helium oxide polymer This type of dielectric material must first be subjected to plasma surface activation treatment, wherein the plasma atmosphere can be a Ν2/Η2 mixed gas, 〇2 or Η2, or Ν2 single gas, and the alkali type solution must be added with a highly oxidizing substance before it can be Complete the deposition of the entire electrochemical metal _ film. 5- The full-process electrochemical electroless plating deposition process of the Shi Xiji dielectric insulating material as described in claim 4, wherein the hydrophobic dielectric material is completely electrochemically deposited. The process, combined with selective plasma treatment and high oxidizing alkaline solution impregnation, can produce “self-alignment” film deposition behavior, selectively producing metal-based film patterns.