TW511135B - Method for integrated in-situ cleaning and subsequent atomic layer deposition within a single processing chamber - Google Patents

Abstract

A system and sequential method for integrated, in-situ modification of a substrate and subsequent atomic layer deposition of a thin film onto the substrate in an evacuated chamber comprising introducing at least one feed gas into the chamber; generating a plasma from the feed gas; exposing said substrate to ions and/or radicals formed by the plasma; modulating any ions; reacting the substrate with said modulated ions and/or radicals to remove any contaminants from the substrate and producing a modified substrate. These steps are followed, in-situ, by performing an atomic layer deposition of a thin film onto the modified substrate in the chamber including introducing a first reactant gas into said chamber; adsorbing at least one monolayer of the first reactant gas onto the modified substrate; evacuating any excess first reactant gas from the chamber; introducing at least one additional feed gas into the chamber, generating a second plasma from the additional feed gas; exposing the modified substrate to additional ions and/or radicals formed by the plasma; modulating any additional ions; and reacting the adsorbed monolayer of the first reactant gas with any modulated additional ions and/or radicals to deposit the thin film.

Description

511135 A7 ___B7___ V. Description of the Invention (I) Cross Reference to Related Applications This invention application claims US Provisional Application No. 60 / 254,280 filed on December 6, 2000, and US Provisional Application filed on December 15, 2000 Benefits of application number 60 / 255,812 and US provisional application number 09 / 812,352 filed on March 19, 2001. BACKGROUND OF THE INVENTION The present invention is basically related to the field of advanced thin film deposition methods widely used in semiconductors, data storage, flat panel displays and related or other industries. In particular, the present invention relates to an on-site pre-cleaning device and technology, which is suitable for depositing conductive, semiconductor and non-conductive thin films with high aspect ratios before depositing conductive, semiconductor, and non-conductive films via modulated ion-induced atomic layer deposition (MII-ALD). Landscape cleanliness and treatment. Detailed Description of Conventional Technology Semiconductor integrated circuit manufacturing is a layer-by-layer process using a series of deposition and etching steps. Lines ("slots") and / or openings ("through holes") are used to connect one part of a line to another, or one layer to another. In aluminum conduction, a flat aluminum film is patterned into a metal line by an etching removal process and then the metal line is isolated using a dielectric gap penetration process. The dielectric system acts as an insulator. In order to achieve the purpose of electrically connecting a bottom aluminum layer and an upper aluminum layer, the dielectric is patterned to form a via, and then the via is deposited with a metal conductor (ie, tungsten). In copper (Cu) conductivity, the grooves and vias are patterned in the dielectric and then __ 4 ___ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) (Please read the notes on the back before filling this page) # 丨 Order ________ Line 1 · _________ 511135 A7 _____ Β7 _____ 5. Description of the invention (>) (Please read the notes on the back before filling this page) Metal conductor (ie copper). The trenches and vias are patterned (and referred to as "single mosaic") and pierced into metal, respectively. In both aluminum and copper conductive techniques, vias are used to connect an upper metal layer to a lower metal layer. However, an important cleaning step must be completed before metal via filling is performed to ensure a reliable, low-resistance electrical connection between the upper and lower metal layers. This cleaning is necessary because before the via filling, the underlying metal guide system is exposed to by-products caused by the etching process used to define the via. Moreover, as a result of being exposed to the atmosphere or any oxygen-containing environment, the underlying metal is oxidized. If the via is used to "contact" the silicon of the device, oxidation of the silicon surface can occur. These oxides (ie, the oxides of aluminum, copper, or silicon) and residues (ie, the carbon-containing residues generated from the photoresist mask in this engraving process) can cause poor electrical connections (ie, High pass. Hole or contact resistance, and poor reliability (ie failure of early electronic displacement). · Wet chemical etching such as buffered oxide etch (BOE) or hydrofluoric acid immersion done at atmospheric pressure The processes have been used to clean the landscape of the patterned dielectric before metal filling. However, when the component geometry is reduced to 0.25 microns or less, the aspect ratio of the via (which is defined (The ratio of the depth of the through hole to the diameter) will increase. In this way, the wet etching will be caused by the unstable cleaning of the bottom of the deep and narrow through hole by wet etching and the possibility of contamination of particles in the cleaning solution. It becomes inappropriate and unattractive. As a result, the argon (Ar) plasma etching performed in a vacuum has been recently used to clean the bottom of the through-hole before passing the metal filling. ..... .............................-. 5丨 丨 ................................................ ............. 丨 丨 丨 丨 ''-丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 This paper standard is applicable to the Chinese National Standard (CNS ) A4 specification (210 X 297 mm) 511135 A7 B7_ -----__ — V. Description of the invention ($) Argon plasma etching is basically a physical sputtering process, because of the excited chloride ion (Α〇. Is used to sputter (that is, physically strike) this unnecessary material such as oxides 'carbon residues' and other impurities. Argon sputtering is more effective than wet chemical etching on the bottom of Jieqitong Efficiency. However, when the vertical and horizontal system is high, the unnecessary material splashed from the bottom of the through hole can be deposited on the side wall of the through hole. This effect will lead to a thin metal layer between the post-deposition ^ and Poor mechanical adhesion between the side walls of the contaminated dielectric vias. In copper conduction, during the copper electroplating process, these re-deposited side wall contaminants can cause voids in the side walls, reducing the effective communication Cross-sectional area of the hole. A reduction in the cross-sectional area of the copper will reduce its current carrying capacity. In addition, the side wall contaminants that have not been removed are mixed like unnecessary material inclusions, so poisoning the Tonghua metal. The effect of these two effects is to increase the resistance of the entire through hole and deteriorate the function of the element. And reduce the reliability of the connection. One of the further disadvantages of the physical argon sputtering is that the shape of the patterned landform can be changed and may affect the design rules of the component. As an example, the top of the through hole is preferentially first It is etched and can be made into a substantially spherical shape (see Figure 3B). A reactive pre-cleaning (US Patent No. 6,11,836) has been proposed to solve the problem caused by pure argon sputtering The aforementioned problem. A halogen or hydrogen-containing plasma system is used to create a process dominated by chemical etching rather than physical sputtering. The halogen or hydrogen containing the substance reacts quickly with the oxide to form an oxygen-containing by-product, which can be pumped down again to be removed. In the next cleaning process, whether it is wet chemical 'argon sputtering or reactive pre-cleaning, the substrate must not be exposed to any oxygen or contain ___6 _______ This paper size applies to Chinese National Standards (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back before filling in this page). · Order 丨 ^ ------- line 丨 # 511135 A7 ___B7____ V. Description of the invention (f)

V An environment with impurities (ie, carbon, chlorine, fluorine, etc.). If such exposure does occur, unnecessary autogenous oxides and / or contamination will re-form at the interface of the newly cleaned substrate, thereby defeating the purpose as a next step before preparation for subsequent deposition. However, when this cleaning method and deposition process are used on separate machines or tools (ie, under wet etching conditions), or on separate workstations in the same cluster of tools (ie, in sputtering or Reactive pre-cleaning conditions) and the wafer conversion of the cluster tool occurs between steps, or at each workstation of the cluster tool. In order to achieve the purpose of solving this problem, an on-site cleaning process using a processing chamber in one and subsequent deposition steps is very much needed. This one preferably has a separate cleaning chamber which is connected to a separate deposition chamber via a vacuum transfer device. Individual cleanrooms can have materials that appear in the surrounding environment at even a reduced pressure, which can negatively affect the interface characteristics of both the patterned dielectric and exposed conductors (that is, the upcoming deposition Subsequent film adhesion and / or lattice direction). The surrounding environment still contains nitrogen-emitting impurities and / or removed pollutants (ie, water vapor, fluorine, carbon-containing residues, etc.), which are part of the previous process step (ie, degassing or precleaning) ) Removed while proceeding. This series is particularly important for low dielectric constant ("low K 値") insulators integrated into copper conduction. Low K 値 materials are sensitive to water and gas and they absorb water easily, so increasing their effective dielectric constant (a low dielectric constant is needed because it can reduce signal carryover that is very close in space). Crosstalk between metal wires and it can result in faster signal propagation). Moreover, low-K dielectric films often show weaker than traditional sand dioxide ___7____ This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) '' one " " (Please read the back first (Notes for filling in this page)

511135 A7 ______B7____ 5. Description of the invention (() adhesion characteristics. As an example, fluorine-doped silicon dioxide (FSG) suffers from poor adhesion characteristics due to the weakly bound interface fluorine (F). Fluorine will destroy the giant (Ta) -containing material often used as a diffusion barrier for copper. A diffusion line property is deposited into the trenches and through holes before the copper seed layer is deposited. The role of the diffusion layer is to prevent Copper diffuses and also acts as an adhesive layer to adhere the copper seed layer to the dielectric layer. Fluoride damage will <strip the effectiveness of the diffusion layer, resulting in a poor barrier effect, High through-hole resistance, formation of copper voids during plating, and delamination (delamination) during chemical mechanical planarization (CMP). The barrier layer is deposited in the same processing chamber Previously, it was highly necessary to immediately have a means to complete a field pre-cleaning / surface treatment step. This method at low substrate temperature due to the low-K material (many The low-K material with K 値 less than 2.5 is only stable at a temperature not higher than 200 ° C to 300 ° C), so this method must be effective. Moreover, we still need to do this An integrated site pre-cleaning process does not introduce any extra complexity into the entire process or trade off the production volume of the deposition chamber. In addition, the integrated site cleaning process should be capable of cleaning and processing with a high aspect ratio. Compared to the bottom and sidewalls of through holes and trenches without causing redeposition or major changes in the landform outline. Invention Summary The present invention is related to conductive, semi-conductive and non-conductive thin films __8 ___ — —_ This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -AW —---- Order— Line 丨 · 511135 A7- ------ B7____ V. Description of the invention (l) A clean-up device and technology for cleaning and processing high-aspect-ratio landforms required before deposition. Surface pollutants to be removed beforehand can be Organic materials, actual contamination, oxides Either unnecessary deposition materials, unnecessary growth materials, or other ways of forming on the surface of the substrate. Surface treatment can be in the form of protection (or removable) of weakly bonded surface types and unsatisfactory surface bonding The form of dots, and / or the modification of the adhesion characteristics of the underlying film with respect to the crystal structure, crystallographic orientation, structure, or bottom film relative to the upper film to be deposited. In particular, the present invention uses a esophagen Or, the most important thing is to eat hydrogen and Veliki or hydrogen ions to clean and treat the bottom of the high-aspect ratio landscape and its walls without the redeposition of pollutants to be removed and negative changes in the contour of the landscape. . This method uses the US application 09 / 812,352 with a filing date of March 19, 2001 in a joint application entitled "For Modulating Ion Inductive Atomic Layer Deposition (MII-ALD)" which is referred to herein as The device described in "MII-ALD Application" became a field-type method without opening the processing chamber door, without substrate transfer under vacuum, and without major changes in hardware. 'The U.S. application is filed at The provisional application if filed on December 6, 2000, and the case number is 60 / 254,280, and the US application here is based on the entire entry. The cleaning surface treatment step is accomplished either by containing a halogen or hydrogen radical alone or by using a low energy ion collision containing halogen or hydrogen and the substrate simultaneously. One-time food-type 5 sees the field, the word system ion induction type. The sub-layer deposition step (or a series of deposition steps) can immediately follow the film containing the desired film (or the modified composition or material that is modified) Lamination) is one of the main elements of suitable precursor materials. —---— 9 ——___ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page). * ··! Order ----- ------ Line #.! 1 511135 A7 ___ B7_; ___ V. Description of the invention (1) The cleaning / surface treatment step can be performed periodically between different layers that are not the same film, that is, change the composition or The individual layers of the material film are completed to enhance the function of the entire stack. The modulation of the cleaning / surface treatment and the deposition step can be controlled by modulation of at least one of the following parameters; the parameter is: ⑴ the flow rate of the precursor substance, 流量 the flow rate containing halogen or hydrogen radicals, ⑶ the ion flow rate, or It is this ion energy. The cleaning / surface treatment and subsequent deposition steps can be performed at low substrate temperatures (ie, generally less than or equal to 200 ° C) to make it compatible with low-K materials. Brief description of the drawings Figure 1 is a deposition system suitable for one of the modulation ion-sensing atomic layer deposition (MΠ-ALD). FIG. 2A is a typical sequential sequence of a modulation-type ion-sensing atomic layer deposition (Mil-ALD) process. FIG. 2B shows another typical sequence of a modulated sequential ion-inductive atomic layer deposition (Mil-ALD) process. FIG. 2C is a typical non-sequential (continuous) modulation ion-sensing atomic layer deposition (MII-ALD) process sequence. Figure 3A shows one of the high aspect ratio vias including an oxidized copper substrate before one of the pre-cleaning steps. FIG. 3B is a high aspect ratio through-hole, which reveals the redeposited sidewalls sputtered with copper oxide and the stepped corners at the corners of the through-holes. FIG. 3C is a high aspect ratio through-hole, which reveals that the copper oxide of the present invention has been removed but has no side wall redeposition and does not adversely affect the through-thickness. ____ ίο ______ This paper size applies to the Chinese National Standard (CNS) A4 Specifications ㈣ x 297 Public Love 1 (Please read the precautions on the back before filling this page) · 1 ^ 1 1 «ϋ nnn ^ eJI nnnn I nn I nn 1 · ϋ nn-511135 A7 _ B7_ V. Description of the invention (( ^) Ladder at the corner of the hole. Figure 4A is a schematic diagram of the present invention, which illustrates a wafer processing system including an integrated on-site cleaning and sink chamber. Figure 4B is a schematic diagram of the conventional technology, which illustrates A wafer processing system including separate cleaning and sedimentation chambers. Symbol description 100 First precursor substance 130 Argon 110 Feedback gas 170 Plasma generation chamber 160 Microwave power 172 Plasma 177 Ion 130 Feedback gas 176 Hydrogen radical 184 Extraction 150 Impedance matching device 170 Plasma source chamber 180 Deposition chamber 171 Dispensing shower head 175 Orifice 181 Substrate 182 Substrate supporting table 202,214 Second precursor substance 11 This paper size applies to Chinese national standards (CN S) A4 size (210 X 297 mm) (Please read the notes on the back before filling this page)

511135 A7 B7 V. Description of the invention) 234 ions 244 substrate bias 315 facets 270,272,274 ion flow 300 copper oxide 305 bottom layer 315 corner 400 first integrated cleaning / deposition chamber 410 second integrated cleaning / deposition chamber 475 cleaning Detailed description of the preferred embodiment of the seed layer of the chamber 450 barrier 455 FIG. 1 illustrates an apparatus suitable for on-site precleaning / surface treatment, which is followed by deposition of Mil ALD. The description of the Mil ALD process and device is described in the Mil ALD application and will not be described in detail here for the sake of brevity. Although the Mil ALD process can be sequential or continuous in nature, the two processes involve the reaction of one of the first and second precursors that undergo ion exposure to enable the ion to transport the required activation energy The activation energy needs to be used to deposit to the close surface atoms and adsorbed reactants through cascade collisions. As previously discussed, the quality of a deposited film is greatly affected by the cleanliness of the substrate surface before deposition. Therefore, in practice, '--- -J2 ---- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) {Please read the precautions on the back before filling this page}

511135 A7 ______B7 _____ 5. Description of the Invention (p) The Mil ALD process must be preceded by a surface cleaning step, and preferably on-site (that is, it is not necessary to transport the substrate from one machine to another). The Mil ALD process and its combined devices are an effective on-site cleaning process in the absence of a first precursor substance and are described below. This is followed by a deposition which introduces the first precursor substance. This integrated field cleaning / surface treatment step is performed as described below. Recourse to Mil ALD's argon 130 (A0 and a halogen-containing feedback gas 110 (ie, Cl2, F2, NF3, etc.), or preferably hydrogen in the absence of a first precursor substance 100 The feedback gas 110 is introduced into the plasma generating chamber 170. Radio frequency (RF) (ie, 400KΗζ, 2MΗζ, 13.56MΗζ, 20MHz, etc.) or preferably a microwave power of 160 (ie, 2.45 GHz or higher) is applied to generate a plasma 172 and through decomposition of the feedback gas 130, 110 to form ions 177 and contain halogen or hydrogen radical 176 (ie, the second precursor substance or reactant ). Atom-containing hydrogen or halogen free radicals 176 will react with surface contaminants such as oxides to form gaseous by-products containing oxygen, which can then be easily pumped out 184 to remove them. Since atomic hydrogen 176 can also act as The reducing agent required for the deposition after forming a metal-containing thin film via Mil ALD, so we best use hydrogen (H2) as the radical feedback gas 110 to form atomic hydrogen radicals 176. Moreover, the atomic hydrogen 176 energy being used Carbonaceous impurities are removed by the formation of gaseous CHx species, and the CHx species can then be easily removed by pumping 184. Preferably the microwave power 160 can be passed through a waveguide, coaxial cable, or ____13 __ paper Zhang scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page)

511135 A7 _ — a __B7__ 5. Description of the invention (lh is other suitable device equipped with a suitable impedance matching device 150 and is attached to the plasma source chamber Π0. Microwave energy can be more efficiently delivered to ionized electrons And obtained the results that have improved the density of the ion 177 and free ion group 176. This is especially true for the generation of atomic hydrogen, .176. Both the stupid ion 177 and the hydrogen atom 176 are transported to the deposition The chamber ι80. The two are also guided at the surface of the substrate 181 through a series of orifices 175 defined on the distribution lotus canopy 171 as shown in FIG. 1. The processing pressure of the deposition chamber 180 Can be maintained in the range of 102 to 1 (T7 Torr, optimally in the range of Loi-icr4 Torr. The showerhead 171 series includes a series or array of orifices 175, and ions 177 and free radicals 176 is transported through the orifice to the substrate 181 and the main processing chamber 180 is isolated from the plasma source chamber as explained in the Mil AU) application. The argon ion 177 will help Good for removal of oxides, carbonaceous matter, and other contamination. Low The impact of the amount of ions 177 promotes the surface reaction between the atomic hydrogen and the oxides (and other pollutants) to form a gas by-product, which can then be easily removed by the pumping 184. The substrate 181 is biased to The energy of the impact ion Π7 is defined. A direct current (DC) or radio frequency (ie, 400KHz, 2MHz, 13.56MHz, etc.) power system is used to bias the substrate support 182. Optimally, the substrate The wiper table 182 is an electrostatic chuck (ESC) to provide effective bias voltage coupling to the substrate 181. A typical substrate 181 bias voltage (V in Figures 2A and 2C; 1,242,282) can The range is -10V to -250V, but is preferably in the range of -10V to -100V, and more preferably in the range of -10V to -50V. Moreover, any of the bias voltage ____14 ---- this paper Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the precautions on the back before filling this page) • ------- Order --------- Line 丨· 511135 A7 _ B7_______ V. Description of the invention &lt; 1) The size and operating cycle can be modulated. The ratio 値 of the argon 130 to the feedback gas of the chamber 110 is basically selected to be less than or equal to 1 'and optimally less than or equal to 0.5. Both the lower argon ion 177 flow rate and the lower argon ion 177 energy can reduce unnecessary facets 515 in the geomorphic corners due to sputtering (see FIG. 3B). The substrate 181 is preferably maintained at less than It is equal to 350 ° C, but the substrate is more preferably maintained at or below 200 ° C, so that the substrate is compatible with very low-K materials. The low energy ion 177 impact system enables the substrate to perform effective cleaning / surface treatment at low substrate 181 temperatures. The cleaning / surface treatment can also be performed in the absence of argon 177 by not allowing the argon feedback gas 130 to flow. However, this may result in a lower decomposition ratio and thus reduce the production efficiency of atomic hydrogen 176. Moreover, the power and thus the removal efficiency of oxides and other contaminants can be reduced due to the lack of the low energy ion 177 impact. Once the oxide, carbon-containing impurities, or other surface contaminants have been removed, the first precursor material 100 is introduced and subsequent thin film deposition is performed using, for example, the MII-ALD application using the disclosed techniques to accomplish this. FIG. 2A discloses a typical sequential modulation of the ion-inductive atomic layer deposition (MII-ALD) process sequence, which includes an integrated field cleaning step completed in the absence of the first precursor material 100. The cleaning step ends at T206, after which the deposition begins. The dashed lines 243, 245 indicate that the bias voltage does not necessarily need to be synchronized with the exposure of the second precursor material 212, 214, but that the bias voltage can be maintained at a constant 値 242 until when it needs to be changed to a Different, V2 244 hours. This site preview _-— -_ 15 __ This paper size is applicable to China National Standard (CNS) A4 (210 X 297 public love) (Please read the precautions on the back before filling this page) · Order ------ --- Line-- · 511135 A7 ------- B7 ____ V. Description of the invention ([^) 淸 Jie Department followed the sequential MII-ALD process. The first and second precursors 202 '214 are sequentially introduced at each deposition cycle. The second precursor material 214 (i.e., hydrogen atom 176) exposure system is consistent with the ion exposure 234 (i.e., Ar + 177) application system and a substrate bias V2 244 application system. The size of the substrate bias | Π | 242 during the cleaning process is typically selected to be lower than the substrate bias | during the deposition process. The size of 244 is to prevent the formation of landforms due to 177 argon ion sputtering. The purpose of the facet 315, and the splashing is performed during the cleaning cycle as disclosed in FIG. 3B. The energy of the argon ion 177 is determined by the bias voltage applied to the substrate 181. A typical substrate bias voltage V2 244 during deposition is in the range of -20V to -1000V but is preferably in the range of -25V to -500V. And more preferably in a range from -50V to -350V in performing the deposition. A modulated DC or RF bias voltage of 185 (ie, 400 KHz, 2 MHz, 13.56 MHz, etc.) can be used. The duration of the cleaning pulse ΊΠ 212 is substantially less than or equal to 180 seconds', preferably from _5 seconds to less than or equal to TΘ12 and less than or equal to 60 seconds. The required film thickness is obtained by repeating the deposition cycle a desired number of times. This second precursor substance exposure duration, T2 214, may or may not be equal to or equal to 212. The variation of the method disclosed in FIG. 2A is illustrated in FIG. 2B and wherein the ion exposure is initiated after the exposure of the second precursor substance. FIG. 2B depicts a sequence of a modified ALD method for periodic exposure combining the substrate 181 to the ion 177. FIG. 2C illustrates a preferred embodiment of the present invention, so it is an integrated on-site cleaning or -------______ which is completed in the absence of a first-driven substance 100. This paper size is applicable to Chinese National Standards (CNS) A4 size (210 X 297 mm) &lt; Please read the notes on the back before filling this page)

511135 A7 ___B7 _ 5. Description of the invention ((ff)

V is a non-sequential or continuous MII-ALD followed by a field processing step. The cleaning step ends at To 254 and thereafter the deposition begins. During the deposition cycle, the first driving substance 100, 110 was not introduced in sequence, but instead the substrate 181 was simultaneously exposed to a first 252 and a second 262 reactant (ie, the optical drive substance) and Undergo exposure to modulated ion 177. In Fig. 2C, the deposition is triggered by turning on and off by modulation of the energy of the impinging ion 177 (optimally controlled by the bias applied by the substrate 181) at a fixed plasma source 160 power. The required film thickness is obtained by exposing the substrate 181 to an appropriate number of pulse periods of the modulated ion energy. As described earlier, the magnitude of the substrate bias | Π | 282 during the cleaning process is typically selected to be lower than the magnitude of the substrate bias N284 during deposition. The ion flux during the cleaning process is 27, i.e., Fi 272, which is typically selected to be lower than the ion flux during the deposition process, i.e., F2 274, in order to prevent spattering during the cleaning process ( That is, the purpose of the landform facet 315 caused by argon ion 177). The ion flux or energy modulation is generally changed from HHz to 20MHz. Moreover, a mechanical lid can be used to periodically shut off the ion source to provide another way to change the ion flux to the substrate. The ion flow rate 270 can be adjusted by increasing or decreasing the flow rate of the feedback gas 130 (i.e., argon) used for the generation of ions 177. For example, the lower flow rate of the feedback gas 130 to the plasma source chamber Π0 will cause the power of a given plasma source 160 to be increased or decreased to change the ion flux 270, and the source Higher power results in greater ion flux 270. The power of the plasma source 160 can be further changed in its frequency, size, and operating cycle __π ._____ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back first (Fill in this page again)

511135 A7 ____B7 __ V. The period of invention description (if), or any combination of the above. Other variations and examples of this subsequent deposition are described in the MII-ALD application in this common application and will not be repeated in detail at this time for the sake of brevity. Basically, the field or cleaning system is completed once before the first deposition cycle is performed. However, multiple cleaning cycles can also be used before each preceding one or more deposition cycles are performed. One example is in the deposition of multiple layers (ie, TaNx / Ta, or Ti / TiN, etc.) or multiple thin film stacks (ie, TaNx / Ta / Cu or Ti / TiN / W, etc.) The cleaning step. Similarly, a deposition sequence can include any number of cleaning steps configured everywhere, even for deposition of a single thin film material. In one embodiment of the present invention, the on-site pre-cleaning process can Used to remove copper on the bottom of high aspect ratios of single or dual damascene structures used in copper conduction (ie, trenches, vias, or overlapping trenches in vias, etc.) Oxide. Simultaneous exposure of the substrate to atomic hydrogen 176 and low-energy argon 177 will result in the removal of copper oxides whose speed is limited by the formation of 0H by-products. And this by-product can then be easily removed by suction 184. FIG. 3A illustrates a still aspect ratio via that contains an oxidized 300 copper bottom layer 305 in a pre-cleaned state. FIG. 3B exposes a high aspect ratio via, which reveals that the side wall surface of the sputtered copper oxide 300 is deposited 320 and is removed at the bottom of the via and the stepped corner of the via corner 315, and the redeposition is Due to excessive argon ion π7 sputtering (the explanation is related to the problems in the conventional technology _18___ __ This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public ¥> ^ ~ '(Please read first (Notes on the back then fill out this page)

511135 A7 ___ B7 __ V. The subject of the description of the invention il)), FIG. 3C has revealed a high vertical and horizontal through hole which reveals the present invention and thus the copper oxide 300 has been removed without side wall redeposition 320 and has not The corner of the through hole is 315 beveled. This same process can also remove carbon-containing impurities left in the etching of a via (either along the side of the via or the bottom of the via). The subsequent deposition of a barrier layer (ie, Ta, TaNx, etc.) formed by the introduction of a suitable precursor-containing material (ie, TaCU 'TaBr5', etc.) tantalum can be accomplished by the MII-ALD method. This same atomic hydrogen 176 is now used as a reducing agent to form macro and by-products of the metal (i.e., hydrogen chloride or hydrogen bromide), which can then be quickly removed by pumping 184. The on-site pre-cleaning step was repeated in performing a barrier stack (ie, TaNx / Ta) and the following sequence was used: (1) reactive pre-cleaning; then (2) TaNx deposition; then (3) Responsive pre-cleaning; Immediately after (4) Giant deposition; Or use the following sequence before the deposition of a subsequent material such as the copper seed layer: (1) Reactive pre-cleaning; Immediately (2 ) Barrier layer deposition; followed by (3) reactive precleaning; followed by (4) copper seed layer deposition. In the above two examples, the sequence of the cleaning and sinking can be completed in the same process chamber 180. However, in this second example, in this ____19 ___ this paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) n He nnnmn A: ennnn -ϋ n in I A 511135 A7 _B7___ _ 5. Description of the invention ([1) The reactive pre-cleaning step before the copper seed layer deposition and the copper seed layer deposition can be completed in a separate MII-ALD chamber In addition, the MII-ALD chamber is integrated into a device capable of vacuum conveying the substrate, so that steps 1 and 2 can be completed in the first integrated cleaning / deposition 400 and steps 3 and 4 can be used as in Inside the second integrated cleaning / deposition chamber 410 of the integrated device shown in FIG. 4A. Since the deposition step is immediately followed by the in-situ reactive pre-cleaning step, no oxide or other impurities can be formed on the cleaned substrate interface. This can result in improved electrical characteristics, reliability, adhesion, surface morphology, crystal structure, and crystal orientation of the deposited film. These advantages are not available in an integrated device using a conventional technology as disclosed in FIG. 4B, where the clean room 475 is separated from the barrier 450 and the seed layer 455 room in FIG. 4B. . The transport of each substrate can have the result that the substrate is exposed to the background ambient gas (even under reduced atmospheric pressure), which in turn will negatively affect the sinking of subsequent films and thus negatively affect the final component function. Moreover, the throughput of the entire system is reduced by the required substrate transport. In addition, system complexity is greatly increased because of the need for a separate pre-cleaning room. Although the example given above is about copper conductivity, a similar integrated field cleaning step can be used to remove any contaminants such as aluminum and oxides at the bottom of high aspect ratio landforms, followed by linear materials such as In-situ deposition of titanium, titanium nitride, etc. is performed using one of MII-ALD (see FIG. 1) titanium, which contains a precursor substance (ie, titanium tetrachloride, etc.), atomic hydrogen 176, and modulated ion 177. exposure. ______20___ This paper size applies Chinese National Standard (CNS) A4 specification (210_ &gt; &lt; 297mm)-(Please read the precautions on the back before filling this page)

511135 A7 V. Description of the invention (f) The first embodiment of the present invention relates to the patterned low-K topography (i.e., high aspect ratio pass) before the subsequent deposition of the upper film (i.e., a barrier layer) is performed. On-site surface treatment of holes and grooves. Atomic hydrogen 176 is effective in removing bonded material and covering the surface of the surface. In this example, halogen is not used. As an example, the atom Hydrogen 176 will absorb loose interface fluorine to form hydrogen fluoride, which can then be easily removed by pumping 184. Fluorine can destroy most metals, especially giants containing metal or metal compounds. In fluorinated materials such as This is particularly useful in the case of FSG. As another example, the low-K material of organic silicides (carbon-doped silicon dioxide) uses methyl (ie, CH3) groups to reduce standard silicon dioxide The dielectric constant of the surface. However, the surface CHx group may be a weak bond and / or occupy an unfilled bond. The atomic hydrogen 176 can fill these bonds through the form of hydrogen bonds, or by forming CHx While removing weak knots Bonding substance, and the CHx can then be easily removed by pumping 184. Substances that bind weakly to the bonding interface deteriorate the adhesion of the upper film (ie, a barrier layer) to be deposited to the dielectric; And the deterioration of the adhesion will lead to the cracking of the barrier layer, copper voids during electroplating, and delamination during CMP. Atomic hydrogen 176 can remove weak bonding surface materials and / or contain carbon, fluorine, and hydrogen ( g 卩, hydrogenated carbon, fluorinated carbon 'PTFE, or Teflon) other types of low kappa membrane protection do not fill the surface bonding points. In addition, the low-K material will easily absorb moisture (ie 〇H substance), the water and gas will harmfully increase the effective dielectric constant of the material, and therefore the capacitance between the conductive material surrounding the dielectric material will also increase the capacitance. Moreover, Table ----- 2J______ This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) Order · Line 丨-511135 A7 V. Description of the invention Poor interface adhesion. Atomic hydrogen 176 can It reacts with the OH interface substance to form water (H20) to improve adhesion, and the water vapor can then be exhausted by air extraction 184. Once the low kappa membrane has been processed, it is passed through MII-ALD and an appropriate optical drive substance (i.e., Giant pentachloride is a barrier material of tantalum). The on-site deposition step is immediately performed. The deposition is completed in the same processing chamber 180, 400. Because of the surface treatment system of the patterned low-k dielectric material landform In order to complete it on-site, subsequent deposition barrier materials will have better interface characteristics (ie, adhesion, conductivity, reliability, etc.) than conventional techniques. This description is used as an illustration but It is not limited to this; further amendments will become apparent to those skilled in the industry after seeing this disclosure and the attached patent application. (Please read the notes on the back before filling this page)

---- Order ---- I -line 丨-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

511135 A8B8C8D8 6. Application scope 1. A sequential method, which is an integrated and in-situ correction of a substrate in a vacuum chamber and a subsequent atomic layer film deposited on the substrate, and the deposition system begins to have an initial The correction step includes: introducing at least one first ion chamber to generate feedback gas into the chamber; generating a plasma from the ion to generate feedback gas to form ions; exposing the substrate to the ions; modulating the ions; The substrate reacts with the modulation ion to remove any contaminants from the substrate and produce a modified substrate; and then the initial modification step to complete the deposition of an atomic layer of a thin film on the modified substrate in the chamber and the modification The steps include: introducing a first reaction gas into the chamber; adsorbing at least a single layer of the first reaction gas onto the modified substrate to extract any excess first reaction gas from the chamber; introducing at least one additional ion to produce The feedback gas enters the chamber, and the additional ion-generating feedback gas can be related to the first ion product. The feedback gas is the same; the feedback gas is generated from the additional ions to generate a second plasma to form additional ions; the modified substrate is exposed to the additional ions; the additional ions are modulated; and the first reaction gas has adsorbed a single layer and The modulated extra ions react to deposit the film. 1 This paper size applies to China National Standard (CNS) A4 specification (21〇X 297 public love) • II,! (Please read the precautions on the back before filling out this page), language 511135 ei D8 VI. Patent application scope 2 · The sequential method as described in the first scope of the patent application, wherein the initial correction step is a cleaning step. 3. The sequential method according to item 1 of the scope of patent application, wherein the correction step is a surface treatment step. 4. The sequential method as described in item 1 of the patent application scope, wherein the initial correction step additionally includes introducing at least one free radical generating feedback gas into the chamber and generating a plasma from the free radical generating feedback gas to form a free radical . 5. The sequential method as described in item 1 of the patent application scope, wherein the atomic layer deposition step additionally includes introducing at least one free radical to generate a feedback gas. Entering the chamber and generating a plasma from the free radical to generate a plasma to Free radicals are formed. 6. The sequential method as described in item 1 of the scope of patent application, wherein the pollutants and dyes include naturally occurring oxides, metal oxides, particulate pollutants, and carbon-containing impurities. _7. The sequential method as described in item 1 of the scope of patent application, wherein the modulation of the ions is modulated in a manner selected from the group consisting of modulating an ion current and modulating an ion energy. 8. The sequential method as described in item 1 of the scope of patent application, which further comprises electrically biasing the substrate to a negative voltage. 9. The sequential method as described in item 8 of the patent application scope, wherein the electrical bias is sensed by a radio frequency power supply. 10. The sequential method as described in item 8 of the scope of patent application, wherein the magnitude of the electrical bias voltage during the initial cleaning step is lower than the size of the _2____ t paper. Chinese National Standards (CNS) A4 specifications (210 X 297 mm) &quot; — ~ &quot; &quot; ** &quot; * &quot; &quot; &quot; ------------- Ilf — (Please read the note on the back first Please fill in this page for more details), \ aj line belongs to 511135 A8B8C8D8 VI. The magnitude of the electrical bias during the patent application of the atomic layer deposition step. (Please read the precautions on the back before writing this page) 11. · If you apply The sequential method described in item 1 of the patent scope, wherein the method is repeated for a thin film deposition layer. 12. The sequential method described in item 1 of the patent scope, wherein the initial correction step is a barrier material film 13. The sequential method as described in item 1 of the scope of the patent application, wherein a copper seed layer is deposited immediately after the initial correction step. H. A sequential method, which is one of a vacuum chamber Substrate and a subsequent atomic layer film deposited on the substrate Integrated and in-situ correction and the deposition system begins with initial correction steps, the method includes: introducing at least one first radical to generate a feedback gas into the chamber; generating a feedback gas from the radical to generate a plasma to Forming a radical; exposing the substrate to the radical; reacting the substrate with the modulated radical to remove any contaminants from the substrate and produce a modified substrate; and then the initial modification step is to complete the atoms of a thin film Layer deposition on the modified substrate in the chamber, the deposition system includes: introducing a first reactant gas into the chamber; adsorbing at least one single layer of the first reactant gas onto the modified substrate; since Any excess of the first reactant gas is pumped out of the chamber; introducing at least one additional free radical generating feedback gas into the chamber, and the additional free radical generating feedback gas may be the same as the first free radical generating feedback gas; 3 Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) &quot; 511135 A8B8C8D8 VI. Application The patent scope generates a second plasma from the additional free radicals to generate a second plasma to form additional free radicals; exposing the modified substrate to the additional free radicals; and an adsorbed monolayer of the first reactant gas with the adsorbed number and The additional radicals react to deposit the film. 15. The sequential method as described in item 14 of the scope of patent application, wherein the initial correction step is a cleaning step. 16. The sequential method as described in area 14 of patent application The correction step is a surface treatment step. 17. The sequential method as described in item 14 of the patent application scope, wherein the atomic layer deposition step additionally includes introducing at least one ion-producing feedback gas into the chamber and generating from the ion. The feedback gas generates a plasma to form ions. 18. The sequential method as described in item 14 of the scope of patent application, wherein the pollutants include naturally occurring oxides, metal oxides, particulate pollutants, and carbon-containing impurities. 19. The sequential method as described in claim 14 of the scope of the patent application, wherein the method is repeated for each thin film deposition layer. 20. The sequential method as described in item 14 of the scope of patent application, wherein the initial correction step is followed by depositing a barrier material film. 21. The sequential method as described in item 14 of the scope of patent application, wherein the initial correction step is followed by depositing a copper seed layer. 22. —A single module system for depositing the atomic layer of a film on a substrate, which includes: 4 square feet £ 1 £ using China National Standard (CNS) A4 (210 X 297 cm) &quot; ...... #. — (Please read the notes on the back before filling this page), l5Jf line belongs to 511135 A8 B8 C8 D8 VI. Application scope Chamber, which includes a plasma generation chamber for generating a plasma, the main chamber also includes an integrated cleaning and sedimentation chamber for cleaning the substrate and depositing the film on the substrate; the plasma generation chamber Is coupled to contain at least one feedback gas to form the plasma; and the integrated sanitary and sedimentation chamber is coupled to contain at least one precursor substance gas. I! I r! #! (Please read the notes on the back first (Fill in this page again) 5 Wire pain This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)