TW201540858A - Systems and methods for generating metal oxide coatings - Google Patents

Abstract

In one aspect, a deposition system is disclosed, which comprises a metallization zone having a sputtering source for generating metal atoms, and a reaction zone having an ion source for generating reactive ions. The system comprises a rotatable mount on which at least one substrate can be mounted, where the rotatable mount is configured for alternatingly moving said at least one substrate between the metallization zone and the reaction zone. Further, the system comprises a movable aperture positioned relative to said sputtering source such that at least a portion of the metal ions pass through the aperture. In many embodiments, the movable aperture is disposed between the sputtering source and the rotatable mount.

Description

System and method for producing a metal oxide coating Related application

The present application is incorporated by reference in its entirety to U.S. Application Serial No. 13/211,884, the entire disclosure of which is incorporated herein by reference.

The invention is generally related to thin film deposition systems. More specifically, the present invention relates to a deposition system having a separate metallization zone and reaction zone for depositing a reaction film.

DC magnetron sputtering is a thin film deposition technique. For example, sputtering can occur in an environment containing argon (Ar). A negative DC potential is applied to the conductive metal "target". A plasma discharge is established to ionize the gas, thereby producing Ar+ ions. The positively charged Ar+ ions accelerate toward the negatively charged target, causing the target to be ejected via sputtering, which in turn produces a metal film on the substrate placed on the opposite side.

The introduction of a reaction gas such as O ₂ or N ₂ allows the film to exhibit the properties of the compound by the reaction between these gases and the deposited metal film. Further ionization and acceleration of these reactive gases can enhance the reactivity of the gas and the membrane in addition to improving the density of the membrane and affecting other membrane properties such as membrane stress, hardness, index and absorbance. Conventional deposition systems are complex and suffer from certain drawbacks, including reduced wafer productivity and material contamination issues, which limit film quality and require extended maintenance of the deposition equipment.

Furthermore, in conventional DC reactive magnetron sputtering (DCRMS) systems for oxide coatings, even small amounts of O ₂ (eg, parts per million (ppm)) target contamination can cause targets. Arcing. Also, if a sufficient reaction gas, such as O ₂ , encounters the target, it causes the surface of the target to be converted into a dielectric/insulator. In this case, the DC power supply may be turned off, thus interrupting the process. Because of these drawbacks, various systems have been developed to monitor the optical properties of the plasma O ₂ and provide feedback to a mass flow controller (Gencoa, Speedflo® or Reactive Sputtering Inc., IRESS) to prevent the target destruction. Other more mechanical means include shielding the magnetron with a high pressure gas curtain. Sometimes this masking is carried out corresponding to a long sputter casting distance and a high pumping speed to prevent arcing. (Scobey, Reactive Magnetron Sputtering Apparatus and Method, CA 2254354 A1).

Therefore, there is a need for improved deposition systems and methods.

One aspect of the invention discloses a deposition system comprising a metallization region having a sputtering source that produces metal atoms, and a reaction region having an ion source that generates reactive ions. The system includes a rotatable mount on which at least one substrate can be placed, wherein the rotatable mount is configured to alternately move the at least one substrate between the metallization zone and the reaction zone. Furthermore, the system includes at least a portion of the metal ion positioned relative to the sputtering source A movable aperture through the aperture. In many embodiments, the movable aperture system is disposed between the sputter source and the rotatable mount.

In many embodiments, the deposition system can include a fence (also referred to herein as a front porch) with a source of sputtering at least partially encircled within the enclosure. The fence can include an opening that provides an outlet for metal ions generated by the sputtering source. The movable aperture is movable relative to the opening of the fence (eg, along a linear dimension) such that the aperture can receive at least a portion of the metal ions exiting the fence via the opening. In many embodiments, the apertures may be substantially labeled with openings to maximize the number of metal ions that can exit the enclosure through the apertures. In many embodiments, the apertures are movable relative to the sputter source to adjust the pressure within the enclosure in which the sputter source is disposed. Moreover, in many embodiments, the aperture itself can form a fence (front porch) in which the source of sputtering is surrounded.

The apertures may be configured to be formed with a fringe plate that moves linearly relative to the sputter source. A variety of mechanisms can be used to move the aperture plates. For example, a plurality of linear motion feedthroughs can be used to move the aperture plate, as described in more detail below.

The sputtering source produces a flow of metal ions that exhibit an angular flow distribution relative to the central axis. For example, the angular flow distribution can be a sinusoid as detailed below. The pores can be utilized to narrow the angular distribution of the flow. As described below, this narrowing of the angular distribution of the metal atoms can be achieved not only by the movable aperture, but also by the fixed aperture relative to the sputtering source to obtain the desired angular distribution of the flow. . In many embodiments in which a movable aperture is used, the aperture can be configured to move along the central axis to narrow the angular distribution of the flow of metal atoms. (Aim the flow). In many embodiments, the pore system is configured to provide an aiming beam of atoms characterized by maximizing the divergence angle, which is equal to or less than about 30 degrees, for example, from about 10 to about 30 degrees.

A wide variety of sputtering and ion sources can be used. In many embodiments, the sputtering source is a magnetron and the ion source is configured to generate O ₂ ions.

In another aspect, the present invention discloses a coated substrate comprising a base substrate (eg, a tantalum substrate), and a metal oxide film (eg, an aluminum oxide film) disposed on a surface of the substrate, wherein the metal oxide film It is substantially free of inert gas impurities (eg, argon, helium, or helium). For example, the concentration of the inert gas impurities in the metal oxide film (coating layer) may be less than 1%, or preferably less than 0.5%, or more preferably 1-10 parts per million. Further, in many embodiments, the metal oxide film can have a thickness of from about 0.1 microns to about 50 microns.

Further understanding of the various aspects of the invention can be obtained by reference to the following detailed description in connection with the associated drawings, which are briefly described below.

10‧‧‧System

12‧‧‧ peripheral bar

14‧‧‧metallization area

16‧‧‧Reaction zone

18‧‧‧ drum

20‧‧‧Substrate

22‧‧‧Magnetron

24‧‧‧Inert gas source

26‧‧‧ front gallery

27‧‧‧ pores

28‧‧‧Outer baffle

30‧‧‧Ion source

32‧‧‧ gas source

34‧‧‧Fence

36‧‧‧Differential pump

38‧‧‧ inner baffle

40‧‧‧Outer baffle

42‧‧‧ hollow cathode electron source

52‧‧‧Main pump

76‧‧‧Anode

142‧‧‧ inner baffle

900‧‧‧ system

901‧‧‧ aperture plate

901a‧‧‧ pore

902‧‧‧Sputter source

902'‧‧‧ bracket

904‧‧‧Fence

905‧‧‧Linear motion feeding device

905a‧‧‧External rotary knob

905b‧‧‧ coupler

905c‧‧‧Internal rod

Pa‧‧‧ pressure

Pb‧‧‧ pressure

Pr‧‧‧ pressure

The above and further advantages of the present invention will become more apparent from the description of the appended claims. The drawings are not required to be scaled, and it is emphasized that the principles of the invention are illustrated.

Figure 1 is a top view of an embodiment of a deposition system in accordance with the present invention.

Figure 2 is a partial cross-sectional view of the deposition system shown in Figure 1.

Figure 3 is a perspective view of an embodiment of a drum that can be used in the deposition system of Figure 1.

Figure 4 is a drawing of an embodiment of a metallization zone that can be used in the deposition system of Figure 1.

Figure 5 is a diagram of an embodiment of a sputtered reticle relative to two substrates.

Figure 6A is a perspective view of an embodiment of a deposition system.

Figure 6B is a perspective view of an embodiment of a reaction zone that can be used in the deposition system of Figure 6A.

Figure 7A is a perspective view of an embodiment of a deposition system.

Figure 7B is a perspective view of an embodiment of a reaction zone that can be used in the deposition system of Figure 7A.

Figure 8A is a diagram of an embodiment of a metallization zone that can be used in the deposition system of Figure 7A.

Figure 8B is a diagram of an embodiment of a metallization zone.

Figure 8C is a diagram of an embodiment of a metallization region having voids formed by aperture masking.

Figure 9 is a diagrammatic partial view of an embodiment of a movable aperture disposed in front of a sputter source in accordance with the teachings of the present invention.

Figure 10 is a graphical representation of the aiming of a sputtered metal atom using a void in accordance with the present invention.

Figure 11A is a diagram showing the collapse effect when a non-targeted metal flow is used to fill a channel, and Figure 11B is a diagram showing the filling of a hole using an aiming flow of a metal atom in accordance with an embodiment of the present teachings.

Embodiments of the deposition system described herein are provided for metal film deposition and subsequent reactions having improved productivity and quality over conventional systems. For example, without limitation, an aluminum film is deposited on the germanium wafer and then successively reacted with oxygen to form Al ₂ O ₃ as a dielectric in the semiconductor component. Other example films are SiO ₂ , TiN and TiC. In addition, the aluminum film deposited on the glass substrate is subsequently reacted with oxygen to form an aluminum oxide film to provide a scratch resistant layer on the glass for consumer electronic applications. A flexible polymer (plastic) substrate can also be used. In other examples, multiple metal film layers are deposited, each having a different refractive index to produce a high quality optical coating. In another example, multiple reactive gases are used alternately to form a SiOxNx material. In another example, a multi-metal target is used and an inert gas is present in the reaction zone to form an accurate multilayer film of X-ray mirrors. Many combinations of metal films and reactive gases can be used in embodiments described herein in a manner that has less material cross-contamination and improved deposition uniformity.

The term "about" as used herein is a variation of the index value of at most 5%, or preferably at most 1%.

Figure 1 shows an embodiment 10 of a deposition system in accordance with the present invention. Embodiment 10 includes a perimeter strip 12 having separate metallization zones 14 and reaction zones 16. The drum 18 has a plurality of substrates 20 attached to the outer surface of the drum 18 such that rotation of the drum 18 causes at least one substrate 20 to alternately pass through the metallization zone 14 and the reaction zone 16. In other embodiments, the drum 18 is replaced by a different shape than a circle. For example, use a hex drum to accommodate a larger substrate. Other drum shapes are contemplated for use in other embodiments to accommodate substrates of different sizes, thicknesses, and shapes.

Metallization zone 14 includes magnetron 22 that is fed by inert gas source 24. The magnetron 22 encircles the front porch 26 and has apertures 27. The pores allow pressure to be introduced into the front porch to accumulate pressure above the reaction zone. The inert gas source is preferably argon, but may be other inert gases such as helium, for example. An outer baffle 28 is provided to assist in maintaining the pressure developed by the gas source 24 to feed inert gas into the metallization zone 14 and exit via a pump (not shown in FIG. 1). The baffle 28 extends adjacent to the drum 18 while remaining separate from the substrate 20 as it rotates through the metallization zone 14. The distance of the aperture from the drum surface 18 also determines the pressure build up in the front porch 26.

Reaction zone 16 contains ion source 30 that is fed by gas source 32. The gas is preferably a reactive gas, including but not limited to oxygen or nitrogen, but may also be an inert gas such as argon. In one embodiment, a hollow cathode electron source 42 is used to inject electrons into the reaction zone 16 to maintain a zero net charge of the plasma neutral or positive and negative charge ions in the reaction zone 16. A pair of inner baffles 38 and outer baffles 40 help maintain the pressure in the reaction zone 16 caused by the inflow of gas from the gas source 32 and exit through a pair of differential pumps 36. Further encircling of reaction zone 16 with fence 34 helps maintain reaction zone pressure. In addition, the metal film deposited on the substrate 20 itself is an additional selective pump for the reactant gases in the reaction zone. The action of both the differential pump 36 and the membrane itself reduces any residual reactive gases to a level that does not perceptibly penetrate into the higher pressure metallization zone 14. The final pumping step is a subsequent selective pumping of any reactant gases entering the metallization zone 14 by the sputtered metal atoms and the gettering reaction on the inner wall of 26. The low mean free path of any O ₂ molecule, such as in the higher argon background pressure metallization zone 14, causes any O ₂ gas to be reacted and inhaled prior to contact with the target.

In one embodiment, system 10 is evacuated to a base pressure Pb and metallization zone 14 is filled with argon to maintain metallization zone 14 at a pressure Pa, 1 x 10 ^-3 to 1 x 10 ^-2 Torr, for example. A reactive gas such as O ₂ flows into the reaction zone 16 via the gas source 32 and is maintained at a pressure Pr, wherein Pr is substantially less than Pa, 1 x 10 ^-4 to 5 x 10 ^-4 Torr, for example. The argon gas in the metallization zone 14 having the magnetron 22 is positively charged by pulsing the plasma discharge with a direct current (DC), pulsed or radio frequency (RF) power supply. The positively charged argon ions strike the metal target disposed on the magnetron 22, causing sputtering of the metal film on the substrate 20 as it passes through the metallization region 14. The substrate 20 is then passed through the reaction zone 16 while the drum 18 is being rotated. The reaction gas is ionized into a plasma by the ion source 30. In an embodiment, the ion source is an electron cyclotron resonance (ECR) plasma source. The substrate 20 having the deposited metal film is then reacted and densified in the reaction zone 16. For example, if O ₂ is the reactive gas in the reaction zone 16, and aluminum is the target used in the metallization zone 14, the aluminum film is converted to Al ₂ O ₃ . The ion source should be understood that system 30 is adapted to contain a reaction gas or the activated species (e.g., O ₂₎ and to accelerate the plasma or ion source of any of the substrate 20 to cause substantially complete reaction of the reaction between the gas and the metal is deposited to form A stoichiometric film or alloy and densification of the film. Figure 2 further illustrates the system described in Figure 1. The argon gas used in the metallization zone 14 and a portion of the reaction gas used in the reaction zone 16 are discharged using a pump, such as a cryopump 52. The portion of the reactive gas that is discharged via the combination of pump 52 and differential pump 36 is controlled by the spacing of baffles 38 and 40 relative to drum 18.

In an embodiment, the system 10 is at a fixed speed The drum 18 is rotated to operate. The reaction gas is set to the pressure Pr to excite the ion source. Adjust the energy and flow rate of the ion source for the desired reaction. An argon gas stream is introduced into the metallization zone 14 and the flow of argon gas is adjusted to the pressure Pa. The magnetron 22 is then energized to form a plasma and the power to the magnetron 22 is adjusted to power P such that each turn of the drum 18 deposits a 5-7 angstrom (Å) metal film on the substrate 20. Substrate 20 is then passed through the reaction zone to react the deposited film, and then the drum is subsequently passed back through the substrate to metallization zone 14 to deposit another metal film. With this method, the film grows rapidly, stably, and predictably because of the linear relationship between the magnetron power and the metal film deposition rate. As the target in the magnetron 22 predictably erodes and the deposition rate decreases, the operator of the system 10 increases the power to the magnetron 22 to maintain a substantially constant deposition rate. In one embodiment, this adjustment of magnetron power is automatically controlled by an algorithm based on the operating time of system 10.

For example, if each drum of the drum 18 is deposited 5A (for example, 5x10 ^-10 m) and operated at 100 rpm drum, a 500 A reaction film is deposited in one minute, and 5000 A is ten minutes. The deposition rate is further limited by the reaction time of the reactive gas, which is further limited by the maximum ion flux or beam current that the ion source 30 can deliver.

A further example of the settings used by system 10 is the use of a three x x six cathode (the cathode is part of magnetron 22 described below) and applies 900 watts of DC power to magnetron 22, which produces aluminum per second. The deposition rate of 32A (the substrate is in the metallization zone). This is called the "static" deposition rate. Typical metallization zones and substrates produced a "dynamic" deposition rate of 1.15 A/rev. for drum 18 rotation at 60 rpm. If the magnetron 22 power is increased to 1500 watts, the static deposition rate will be approximately 1.66 compared to the rate of 900 watts, resulting in a static deposition rate of 53 A/sec. In one example of system 10, a dynamic rate of 5 A/rev. of aluminum was deposited using a magnetron power of 3.6 kW and a drum 18 rotation rate of 60 rpm. 20 of the substrate 16 through the reaction zone, the oxygen O ₂ ⁺ the reactive flow must be maintained at sufficient size to deposit the aluminum film is converted into a stoichiometry of Al ₂ O _3. According to the molecular formula of Al ₂ O ₃ , more than 50% more O ₂ than aluminum is required to completely react the film. For example, the metal deposition rate of 5 A/rev. corresponds to a metal flow rate of 3 x 10 ¹⁵ atoms/cm ² /sec. at a drum 18 operating rate of 60 rpm. A similarly sized O ₂ ionization flow rate having an average energy of about 30-60 eV/atom is used. It is important that the upper limit of the eV/atomic energy is not exceeded because the re-sputtering of the deposited film interferes with the deposition process. In addition, beyond this energy threshold, the energy ions will sputter the film portion, causing non-stoichiometric film or implanted into the film, thus causing local stress defects. This upper limit is determined by the specific film deposited.

Since the reaction time in reaction zone 16 is limited by ion current or flow, it is important that ion source 30 be as close as possible to substrate 20. The linear ion source may be closer to the substrate 20 than a series of circular ion sources disposed along the height of the drum 18. If a circular ion source is used, the ion source must be placed above the substrate such that the ion source height and separation distance from the substrate 20 results in a uniform flow distribution across the substrate (which is the sum of the individual ion sources). For example, for a drum 18 of approximately three feet height, the ion source should be 5-8 inches above the substrate. This is not possible for multiple circular ion sources due to ion beam overlap problems. In contrast, the magnetron 22 need not be so close to the substrate 20 because the magnetron 22 can support a large power density.

The proximity of the ion source 30 to the substrate 20 and the baffles 38 and 40 against the drum 18 limits the thickness and curvature of the substrate 20. In this case, the drum 18 can have a rest-processed or recessed surface with its contents placed on the substrate 20. Figure 3 shows the drum 18 with the return working surface of each substrate 20. In one example, the top of the substrate 20 is "pound" (eg, flush) to the surface of the drum 18. Further variations in drum shape are considered to be within the scope of the invention, including replacing the substrate with another target to receive the metal film.

The uniformity and stress of the film deposition are further enhanced by adjusting the pressure Pa in the metallization zone 14 and the distance from the target to the substrate 20 or the pressure-distance product (P x Tsd). Adjusting the Tsd is facilitated by placing the magnetron 22 within the flange housing having the adjustment rod 72, as shown in FIG. The push rod 72 is adjusted to move the magnetron 22 closer to the substrate 20 disposed on the drum 18. In the preferred embodiment, magnetron 22 includes a reticle 82 between target 78 and substrate 20. The anode 76 is disposed between the target 78 and the cathode 74 and is designed to have a small annular portion between the target 78 and the substrate 20. In one example, the anode is biased to ground potential and the cathode 74 in electrical communication with the target 78 is biased to a negative potential that is less than the ground potential. A positively charged inert molecule (such as Ar+) accelerates toward the negatively charged target 78 and strikes the target, causing sputtering.

In order to achieve optimum uniformity of the deposited material on substrate 20 using a linear magnetron, the magnetron length should be substantially equal to the height of drum 18 plus twice the target width. For example, if the height of the drum 18 is one meter and the width of the magnetron is 10 cm, the length of the magnetron should be about 1.2 meters. In one example, the inflow and outflow of gas source 24 and the supply of magnetron 22 are selected. The bulk line essentially eliminates the pressure gradient along the length of the magnetron, thus increasing the linear uniformity of the film.

In the preferred embodiment, the reticle 82 shown in Figure 5 is used to enhance deposition uniformity. The photomask 82 is interposed between the magnetron 22 and the substrate 20 to form a local film variation. For the flat substrate 20, the reticle 82 produces a linear wavefront of the sputter material to the substrate 20. Various variations of the reticle are used to match the shape of the wavefront to the surface of the non-planar substrate, such as a convex or concave substrate. Figure 5 further illustrates the positioning of the reticle 82 just exiting the metallization 14 and the substrate 20b within the metallization 14 relative to the substrate 20a. The uniformity of the deposited metal film mainly determines the uniformity of the film of the reaction. This is because the ion source 30 is typically operated in a saturated mode. In other words, a little more current is delivered to the ion source 30 than necessary to cause saturation of the stoichiometry of the membrane. For example, if the voltage of the ionized reaction gas is kept sufficiently low (e.g., less than 100-125 eV), the molecular bonds of the deposited reaction membrane do not break and remain stoichiometric in the reaction membrane. Once the stoichiometry is reached, the membrane is stable. In embodiments where system 10 is configured to produce an alloy, ion source 30 is operated at a setting between zero kinetic energy and less than saturation to obtain a film of any composition.

In one embodiment, the drum 18 is cooled with a liquid, such as water, with an applied RF, DC or pulsed electrical bias to enhance activation or to facilitate planarization of the substrate having the photolithography via re-sputtering. The linear magnetron 22 of the present invention can be readily adapted to hide the anode 76 design as shown in FIG. In previous solutions using reactive sputtering, the anode was also a substrate and was coated with an insulator. Therefore the electrons in the plasma It no longer returns to the ground potential, and the accumulation of charge causes the plasma to spread out to the substrate, seeking a way back to the ground potential. At this point the magnetron plasma is in contact with the substrate, which causes undesired substrate heating. The hidden anode 76 as shown in Fig. 4 overcomes this problem because the anode is not coated with an insulator, which in turn keeps the plasma confined to the target 78, thus reducing substrate heating.

In the previous solution, the magnetron 22 was deliberately operated in an unbalanced mode. In this mode, the plasma is extended to the substrate 20, so ions are added from the argon ions in the magnetron plasma to assist the substrate. This plasma extension provides membrane and gas reactivity, however it is combined with a metallization zone. In this unbalanced configuration, high power and high film deposition rates place severe limits on substrate temperature and corresponding cooling requirements. Unlike the previous solution, the present invention separates the metallization zone 14 from the reaction zone 16 in an efficient manner.

In the preferred embodiment, substrate 20 is disposed vertically, as shown in FIG. 3, and at this point a linear magnetron 22 is used to deposit the film. Simultaneously in the metallization zone 14 at the deposition flow, each point on the vertical line of the substrate takes the same amount of time, thus substantially eliminating the center-to-edge film thickness variation or gradient along the substrate 20. Previous solutions that were hampered by this film gradient required the use of delta-shaped magnetrons to produce a uniform film with increased cost and system complexity. Even with the use of delta-shaped magnetrons, a mask is needed to improve uniformity. In the present invention, such a gradient does not exist, so a standard linear magnetron and a standard target can be used.

Due to the complete separation between the metallization zone 14 and the reaction zone 16, the system 10 operates with a very small open loop of each zone and has no risk of reactive sputtering lag, its "poison" or oxidized metal target. Event 78, the result is interrupted by the sputtering process. Further separation of the zones avoids the use of pulsed sputtering or other means to reduce the need for arcing events due to target poisoning, although pulse sputtering is used in one example to enhance ionization of the target imparted to the properties of the film. As a result of the separation of the metallization zone 14 from the reaction zone 16 and the reduction of the target poison, it is necessary to separate the pressure differential of each interval of about one order size and the entity of the mean free path of the reaction gas. In one example, the metallization zone 14 has a pressure Pr of 1 x 10 ^-3 Torr while the reaction zone 16 has a pressure Pr of 1 x 10 ^-4 Torr. This difference in pressure differential and mean free path provides a diffuse gas barrier to further enhance the isolation of the two zones. It is contemplated that larger distances between the two sections may also reduce pressure differentials and various combinations of pressure differentials and entities are within the scope of the present invention. The present invention overcomes the limitations of previous solutions that require an optical plasma spectrometer or mass flow controller feedback loop to control the complex feedback loop of gas flow and magnetron power supply.

The present invention also overcomes the limitations of the prior art where it is desirable to incorporate the cathode of the magnetron into the differential pumping enclosure rather than merely enclosing the reaction zone 16 in the differential pumping enclosure. The method advantageously facilitates a system having a multi-metallization zone because only the general reaction zone 16 is differentially pumped as shown in Figures 6A and 6B. In Figure 6A, system 90 has a fence 12 having an opening 92 of ion source 30. Reaction zone 16 is loaded into fence 34 and differentially pumped by pump 36. In FIG. 6B, the fence 34 includes a pair of inner baffles 38 and a pair of outer baffles 40. The differential pump 36 is positioned outside the inner baffle 38 and inside the outer baffle 40. Reaction zone 16 is within inner baffle 38.

Pump 36 and baffles 38 and 40 are selected such that the pressure outside reaction zone 16 (between reaction zone 16 and metallization zone 14) is reduced to substantially less than the pressure of reaction zone 16, such as 1 x 10 ^-5 Torr. In this case, if the pressure outside the reaction zone 16 is Pr and the conductivity of the baffle is Cb (measured in Torr-liter/sec) and the pressure reduced outside the fence 34 is Po, the speed of the pump 36 is in the equation S pump = (Pr-Po) / Cb calculated. By encircling the reaction zone 16 and separately pumping this zone separately from the rest of the system, the pump size and system size are reduced, allowing the target to be more loosely coupled to the ion source.

In a preferred embodiment, reaction zone 16 includes an additional pump 112 positioned between inner baffles 38, as shown in Figures 7A and 7B. With the addition of pump 112, movable baffles 38 and 40 are closer to drum 18 to improve isolation of the reactive gases from the rest of the system. In another embodiment, moving the pair of inner baffles 38 closer to the drum 18 and moving the outer baffle 40 further away from the drum 18, so that the differential pump 36 providing differential reduction of the reactive gas can be used at this time. The inert gas is evacuated from the metallization zone, thus eliminating the need for the pump 52 shown in Figure 2. The speed of the pump 112 is limited by the conductivity of the apertures created by the velocity of the outer baffle 40 and the pump 112.

With the improved isolation of the reactive gases shown in Figures 7A and 7B, the linear magnetron 22 can be positioned further away from the substrate 20, as shown in Figure 8A. This advantageously further reduces the particles on the substrate 20. Since the inert gas is locally introduced into the magnetron 22, the open region through which the inert gas is evacuated is effectively a sputtering void having a conductive Ca.

Figure 8B shows an embodiment of the metallization region 14 in which the plasma from the magnetron 22 is substantially confined by a pair of inner baffles 142. Figure 8C shows a preferred embodiment of the metallization region 14, wherein the plasma is limited by the apertures 27 formed by the aperture shields 26. If the pressure in the sputter front gallery 26 is fixed at the pressure Pa and assuming that the main pump 52 is at a much higher speed than the differential pump 36 and the main pump 52 has a speed P _speed , the size of the aperture can be calculated to maintain Pa. The distance of the aperture plate from the substrate holder (e.g., drum) 18 also contributes to the pressure build up in the front porch 26.

The vertical orientation of the deposition in the metallization region 14 advantageously reduces the likelihood of particles falling on the substrate 20. Unlike prior solutions using down-facing deposition, the need to shut down the system for maintenance is reduced and the use of a comprehensive erosion target is eliminated to minimize target redeposition. The Δ magnetron used in the previous solution has a long meandering non-sputtering zone which becomes saturated with the redeposited film. Due to the stress, the film "skins off" over time, which greatly aids in the undesirable particles reaching the substrate 20. The particles in the thick coating are reduced by using a linear magnetron 22 whose re-deposited area is substantially smaller than the Δ magnetron.

A further advantage of having a single layer of deposition, and a high velocity through the zone of inert gas and subsequent conversion to a dense stoichiometric reaction layer 10 is to significantly reduce the inert gas in the substrate 20. By reducing the inert gas (e.g., argon) in the substrate 20, the stress variation caused by the defects is greatly reduced. The reaction film stress is then controlled by film densification by a process known as atomic hammering of the ion source. Stress control is achieved by controlling atomic/ion ratios (e.g., metal atomic flow versus ion flow ratio) and momentum exchange of ions at the surface. By controlling the magnetron 22 power, the anode 76 current and the anode 76 voltage, the film stress can be varied or controlled, or the magnetron 22 power, the anode 76 current and the anode 76 voltage can be maintained constant, and then by changing The drum 18 is rotated at a speed to control the atom/ion ratio and metal rate of the drum 18 for each revolution.

In one embodiment, a second magnetron is added to system 10 to form a high and low index metal oxide layer on substrate 20 to produce a high quality optical coating. For example, a target in a magnetron and a target in the second magnetron can provide any number of SiO ₂ /Ta ₂ O including anti-reflection, band batter and barrier coating. ₅ optical coating. The formation of the optimized layer can be easily monitored by an optical monitor with a gate. Other embodiments use more than two magnetrons to provide a more complex structure. In another embodiment, the precise metal is rapidly formed from the low Z material of the X-ray mirror using two magnetrons each having its own metal target and the reaction gas in the reaction zone 16 is replaced by argon gas. Multilayer film.

In another embodiment of the multilayer coating, an additional (e.g., second or more) magnetron is disposed within the single attachment front porch 26. Use an additional magnetron and indicate it with the motor controller. In this way, layer A is deposited using magnetron A, then paused, and then magnetron B is rotated at the position before the aperture, and electric power is applied to magnetron B to redeposit film B. The multi-target sputtering system of this embodiment greatly reduces the mechanical footprint and cost to the owner.

In another embodiment, the gas source 32 is pulsatingly or alternately adjusted between different gases to form different combinations of membrane materials. For example, using a ruthenium target, O ₂ and N ₂ reaction gases are sequentially used to produce SiN and SiO ₂ layers. Alternatively, an O ₂ /N ₂ mixture is used to form the SiON _x material.

The aperture 27 disposed in front of the magnetron sputtering source, as shown in Figure 1, can have many different functions. For example, pores can cause sputtering gases (such as The pressure of argon gas accumulates in the magnetron front porch (in some embodiments, the sputtering gas can be fed directly into the magnetron front porch). This pressure gradient can contribute to the shielding (isolation) of the sputtering zone of the reaction zone (e.g., the oxidation zone described above), which can be reduced, preferably to eliminate contamination of the target by reactive gases such as oxygen.

In some embodiments, no pumping is applied directly to the magnetron front porch. In such embodiments, the spacing and aperture of the rotatable mount (eg, the drum described above) and the pore size combined with the pumping speed of the chamber pump (eg, pump 52 shown in FIG. 2) may determine the magnetron front porch The rate of pumping on the sputtering gas (e.g., argon), thus determining the amount of pressure build up in the front porch of the magnetron.

For example, in some embodiments, wherein the sputtering gas is argon and the reactive gas is oxygen, the pores can accumulate high argon pressure on the sputtering target (cathode). For example, if sputtering is performed at 10 mTorr and the oxygen (O ₂ ) pressure in the ion source is ₂ x 10 ^-3 Torr, it can be between the sputtering source and the ion source (for example, between the sputtering zone and the reaction zone). A pressure gradient greater than 10 is developed, thus inhibiting reactive ions, such as oxygen ions, from penetrating into the sputtering zone.

Furthermore, the separation of the sputter zone from the space of the reaction zone can further shield the two zones from each other, thus inhibiting cross-contamination therebetween. For example, in some embodiments of the invention, an ion source that produces reactive ions (eg, O ₂ ions) is disposed at a location opposite the sputtering source such that the ion source is rotatable relative to the sputtering source. The perimeter of the stent is angularly separated by 180°. In certain such embodiments, the ion source can comprise a reaction chamber in which a reactive gas such as O ₂ can be fed.

Another advantage is provided around the fence of the magnetron and the pores, that is, if any reactive gas such as O _{2 is} found to enter the path of the magnetron fence, it can be quickly aspirated by the forward sputtering flow. To the surrounding walls of the fence and / or the aperture plate. In other words, the infiltrated reaction gas can be effectively extracted.

In some embodiments, as shown in FIG. 9, the system 900 for producing an oxide coating according to the present invention comprises a sputtering source 902, such as a magnetron (in this figure, a reaction is not depicted). Zone) the front movable aperture 901a. In this embodiment, the aperture 901a is in the form of a rectangular opening formed in the aperture plate 901. The aperture 901a can serve as an output opening around the fence (front porch) 904 of the magnetron. In some embodiments, the fence itself may include an opening through which the metal atoms may exit the fence, and the aperture 901a may be placed before the opening, preferably as substantially marked. The movable aperture 901a can be configured to move rearwardly and forwardly along the axial direction, which can correspond to the central axis of the flow of metal atoms generated by the sputtering source and toward the aperture. Similar to the previous embodiment, system 900 includes a rotatable mount 902' on which a plurality of substrates 903 can be placed. In this embodiment, the substrate is disposed on the rotatable support such that when the substrates are aligned with the apertures 901a, the axial direction is perpendicular to the substrate surface.

A variety of mechanisms can be used to move the aperture plate relative to the sputter source and the rotatable mount. For example, in this embodiment, a sputter source (eg, a magnetron) is enclosed within a fence 904. A series of linear motion feedthroughs 905 are coupled to the aperture plate 901. Each linear action feedthrough 905 includes an external rotary knob 905a that is external to the fence 904 (in this embodiment, outside the vacuum chamber), which may be, for example, manually or by motor To rotate. The coupler 905b couples the rotary rotation of the knob to the inner rod 905c, which is fastened in the fence and coupled to the aperture plate at its distal end, and then rotates the outer section of the knob into a linear shape of the inner rod 905c. The action, which in turn causes a linear movement of the aperture plate and a linear movement of the aperture. A wide variety of commercially available linear motion feed devices can be used, such as those marketed by MDC Corporation of Haywood, California. In this embodiment, four linear motion feed devices are used, although Figure 9 shows only two.

The movable aperture can adjust the pressure within the sputter source front gallery (chamber) 904, for example, it can form a fence around the magnetron. For example, for a given flow rate to a sputtering gas (such as argon) in the front gallery of the sputtering source, the closer the pores are to the sputtering source, the higher the pressure of the gas within the chamber. Variations in the pressure in the front gallery of the sputter source can be used to adjust the stress of the metal film sputtered onto the substrate, for example, from compressible to stretchable stress. For example, in certain embodiments, the stress of a sputtered metal film can be compressed at very low pressures (eg, a pressure of 0.75 to 2 mTorr) at high pressures (eg, pressures greater than 30 mTorr) The stress can be stretched.

In a conventional ion assisted sputtering system for producing a coating, the sputtering gas and the reactive gas system are in communication with each other in a single chamber. As a result, it may not be possible to vary the operating pressure of the sputtering source and the ion source over its entire individual operating range. For example, in an entire range in which the pressure of the sputtering gas in the magnetron can be changed, the ion source (for example, an O ₂ ion source) may not perform well. For example, in many cases, the maximum operating pressure of the ion source can be about 1 mTorr, which is less than the maximum operating pressure of the magnetron, for example, 30 to 50 mTorr. In the system according to the present invention, since the sputtering source is isolated from the reactive ion source, the pressure of the sputtering source (e.g., magnetron) and the pressure of the ion source can be independently varied. For example, the pressure of the sputter source can vary over its entire operating range without negatively affecting the operation of the ion source. For example, in some embodiments of the invention, the movable aperture is disposed in front of the sputter magnetron (see, eg, Figure 9), the magnetron pressure (eg, magnetron front porch) The pressure inside can be moved by the moving aperture plate (by the aperture) close to or away from the rotatable support (which reduces or increases the pumping speed applied to the magnetron front porch, with the pressure of the sputtering gas (eg argon)) Increasing or decreasing) and varying the flow rate of the sputtering gas (eg, argon) over its entire operating range. This change in the magnetron front porch pressure has no detrimental effect on the operation of the ion source due to its isolation from the magnetron.

In some embodiments, the independent control of the sputtering gas pressure and the reaction gas pressure independently adjusts the stress of the sputtered metal film generated in the sputtering zone and the oxide generated by the oxidation reaction of the metal film in the reaction zone. The stress of the membrane. For example, in certain embodiments, the metal film can be deposited onto the substrate in a stretchable, compressible or neutral stress state. The pressure of the reactive ion source (e.g., O ₂ ion source) can then be controlled to produce a metal oxide in the desired stress state. In other words, the stress of the metal and oxide film can be separately adjusted to have an unprecedented control over the adjustment of the stress of the resulting metal oxide film (e.g., aluminum oxide film). For example, if the metal film is sputtered onto the substrate in a compressible state, the pressure of the reactive ion source can be adjusted to produce a metal oxide film with a net zero stress. Generally, as the ion energy increases, the compressive stress of the resulting metal oxide film also increases. For example, if the metal film is generated in a tensile stress state during the sputtering phase, the energy of the reactive ions (eg, O ₂ ions) during the reaction phase may increase to offset the tensile stress to produce a slight A metal oxide film that compresses stress or neutral stress. In certain embodiments, the energy of the reactive ions (eg, O ₂ ions) can range from about 65 to 150 eV.

In certain embodiments, the system in accordance with the present invention causes the pressure of the sputtering gas (e.g., argon) to be adjusted based on the desired stress of the deposited metal film. In some embodiments, the pressure of the sputtering gas (eg, argon) may be pulsatingly adjusted to average metal film stress in the sputtering front gallery via the process cycle (or at least a portion thereof). For example, the argon pressure in the magnetron front porch can be varied during different sputtering cycles because the substrate placed on the rotatable support passes through the sputter zone multiple times to achieve the desired average metal stress. In some embodiments, the sputtering pressure can be adjusted to impart tensile stress to the metal film. In other words, the metal film is deviated by the tensile stress. Since the ion source can be operated independently of the sputtering source as described above, the ion source, the pressure including the reaction gas, and the energy of the reactive ions can be assembled in view of the tensile stress of the metal film to assemble the resulting metal oxide film. The stress is adjusted to the desired value. For example, the ion source can be assembled to bias the metal film to a lesser stretched state, which, in combination with the tensile bias provided by the sputtering source, can result in a metal oxide having a neutral or slightly compressible stress state. membrane. This stress adjustment of the resulting metal oxide film has benefits in a variety of applications, including depositing a metal oxide film (e.g., aluminum oxide) on a flexible substrate, such as a plastic substrate.

In some embodiments, the apertures, fixed or movable apertures used in the system according to the invention can be used to target sputtering atoms. For example, referring again to Figure 9, the aperture 901a is movable relative to the magnetron such that the maximum divergence of atoms passing through the aperture to the substrate is less than the desired threshold. The angular distribution of the flow of the sputtered atoms emitted is characterized by a sinusoidal function. For example, the emitted flow may be characterized by =Cos ⁿ , which represents the angle relative to the central axis of the flow (eg, the axial direction depicted in Figure 9) (which may be perpendicular to the leading atom) Substrate) The flow rate of the sputtered atoms. For larger values of n (eg, n is greater than about 3), the flow tends to concentrate more, while for small values of n (eg, n is less than about 3), the flow spreads or "squashed."

Referring to Fig. 10, without the aperture 901a, certain atoms emitted at a large angle (e.g., angles θ ₁ and θ ₂ ) perpendicular to the substrate will strike the substrate at a high incident grating angle. The atoms striking the surface of the substrate at a high grating angle are liable to be poorly attached to the surface of the substrate. With the aperture plate 901 in place, these vacant atoms impinge on the aperture plate and are thus prevented from reaching the substrate. More specifically, in this embodiment, atoms emitted at an angle greater than θ ₃ strike the inner surface of the aperture plate and thus cannot reach the substrate. In other words, in this embodiment, the pores reduce the diffusion of the angular distribution of the atoms by ensuring that the maximum divergence of atoms emitted through the pores is θ ₃ . The maximum angular distribution of the emitted atoms can be adjusted by moving the apertures in a direction perpendicular to the substrate. As the diffusion of the angular distribution of the emitted atoms narrows, the number of atoms leaving the pores decreases, thereby reducing the deposition rate of atoms on the substrate. This adds a practical limit to the minimum spread of the angular distribution of the emitted atoms. In some embodiments, the aperture plate is positioned at a maximum divergence angle of atoms that can be emitted as it exits the aperture, i.e., θ ₃ , in the range of from about 10 to about 30 degrees. In some embodiments, a series of plurality of pores (eg, 2 to 5 pores) may be placed spaced apart from each other to adjust the angular diffusion of the emitted atoms rather than a single pore. In some embodiments, the use of a plurality of apertures further reduces the angular spread of the emitted atoms beyond what is actually achievable using a single aperture.

The aperture plate can be designed to achieve the desired aiming of the emitted atoms by using a variety of different methods, i.e., the angular spread of the atoms is characterized by a maximum divergence angle. For example, in some embodiments, the pinhole method can be used to measure the angular distribution of the cathode flow of a particular magnetron. The measured angular distribution and the established separation of the cathode from the pores can be used together to design a planar size plate. Further details regarding the pinhole method can be found in J. A, Thornton and D. W. Hoffman JVST 18, 2, March 1981, which is incorporated herein by reference in its entirety. In some cases, the size obtained by measurement can be further optimized by taking into account the conductivity of the pores, the gas phase scattering in the front porch, and the theoretical model of the distance between the pores and the rotatable scaffold.

The use of apertures in accordance with the present invention to target atoms emitted from a sputter target provides a number of benefits. In some applications, this aiming can provide improved results in the planarization of the microelectronic structure. For example, the use of atoms that are not emitted in accordance with the present invention to planarize or fill the cells or trenches results in atomic deposition on the top of the cells around the edges of the openings, thereby causing the top of the cells to collapse (the tearing effect) ( Tear drop effect), which will hinder the filling of the bottom of the tunnel, as shown in Figure 11A. Conversely, the use of voids in front of a sputter target, such as a channel or trench, can result in a more uniform deposition of sputtered atoms. In particular, adding a hole in front of the sputtered substrate The high angle incident atoms can be greatly reduced to reach the substrate. In some embodiments, high angle incident atoms from the sputter flow rate can be removed almost completely using a plurality of apertures placed in a series and spaced apart from one another by a predetermined distance (distances). In other words, with aiming, metal atoms that are incident at a high angle with respect to a direction perpendicular to the substrate can be eliminated. The arrival of metal atoms in the angular distribution relative to the smaller incident angle of the general can completely fill the channels or trenches, as shown in FIG. 11B. The filled channels or trenches can be subsequently planarized, for example, by chemical mechanical planarization.

As noted above, the isolation of the metal sputter zone from the reaction zone in accordance with the present invention provides a number of advantages. As described in more detail below, another advantage of this type of isolation between the two zones is that it can be greatly reduced, in some cases eliminating the oxidation of the metal from the sputtering gas (ie, the gas in the front of the sputtering front). (The sputtering gas is usually argon, although other inert gases such as helium or neon may be used). This is in turn reduced, and in some cases eliminated, the resulting metal oxide film (coating) is contaminated with a sputtering gas, such as argon. It is known that the inclusion of impurities in a metal film sputtered onto a substrate results in a compressive stress component in the film, particularly at higher cathode voltages. In many cases, the sputter impurity is an argon atom. In particular, at low sputtering pressures (e.g., a pressure of from about 0.5 to about 5 milliTorr), the full potential neutral argon atoms at the cathode will reflect off the cathode and can be implanted into the substrate to cause compressive stress. At higher sputtering pressures, there is a possibility that a sputtering gas (eg, argon) is implanted into the active growth layer below. By utilizing the teachings of the present invention, particularly by isolating the sputtering source from the ion source, this component of the compressible stress in the resulting metal oxide film can be reduced and preferably eliminated. Furthermore, The ion source can be used to control the stress in the metal oxide film in a repeatable and controllable manner, for example, in the manner described above.

In conventional batch or load-locked sputtering processes, reactive or non-reactive or ion-assisted deposition, sputtering gas (which is typically argon) is always present in the process gas and throughout the film deposition cycle The process gas is in continuous communication with the substrate. Thus, for larger than single layers (1 monolayer 1 atomic material layer), argon has the opportunity to be entrained or captured into subsequent layers of the substrate.

Conversely, in many embodiments of the invention, only one single layer of metal can be deposited per revolution of the rotatable mount. A single layer of metal is deposited by a subsequent exposure to a reactive ion, e.g., _2, and completely consumed by the oxidation or O produced in the ion source of 100% O ₂ operation. Thus, in many embodiments, due to the thinness of the coating, no argon atoms, or O ₂ molecules, are implanted into these very thin metal layers. Thus, in many embodiments, the substrate does not have any implanted argon atoms. For example, in certain embodiments, the concentration of argon atoms in the resulting metal oxide film can be less than 1%, or preferably less than 0.5%, or more preferably from 1 to 10 parts per million.

In many embodiments, after deposition of the metal film, during the reaction of ions, for example, O ₂ ions during the oxidation phase, any free argon atoms remaining on the surface of the film may be strongly reacted by impacting the surface of the metal film. (for example, O ₂ ions) removed. Furthermore, as described above, since the accumulation of the metal oxide layer on the surface of the substrate under the processing is achieved by periodically depositing a thin layer of metal followed by reaction of those layers with reactive ions (for example, O ₂ ), In many embodiments, no argon gas is buried in the multilayer reaction film below. Therefore, the resulting oxide film (for example, an aluminum oxide film) is substantially free of sputtered gas atoms (for example, argon atoms).

By ensuring that substantially no sputtered gas atoms (for example, argon atoms) are incorporated into the oxide film formed on the surface of the substrate, the stress associated with the sputtered gas atoms can be removed as impurities in the film. Ingredients. This can also be significantly reduced, preferably eliminating the effects of voltage variations in the sputtering source (eg, magnetron), which can occur throughout the life of the target and also with the pressure build-up on the oxide film. occur. As a result, the stress of the resulting metal oxide film can be determined to the first order by the energy of the reactive ions striking the substrate and the flow rate of the reactive ions. In some embodiments, the discharge voltage and discharge current of the ion source can determine the energy of the reactive ions and the ion flux.

In some embodiments, the stress in the ion assisted membrane process can be determined by the ion to atomic ratio. In these embodiments, the stress can be controlled by the rotational speed of the rotatable mount, the ratio of magnetron power (metal rate/rotation) and ion beam current. More generally, the quality of the film, such as the refractive index of the metal oxide film, optical transmission and mechanical stability can be affected by the ion/atomic ratio. In many embodiments, the ion/atomic ratio is about 1, preferably greater than 1, for example, from about 1 to about 10.

As a result, the coated substrate produced includes a base substrate and a metal oxide film disposed on the surface of the substrate. The membrane can be placed on multiple surfaces and these can be the same or different. Various substrates can be used, including, for example, crystalline materials such as ruthenium and sapphire, flexible materials such as polymer substrates and various plastics, including polycarbonate or polymethyl methacrylate, and glass such as Soda-lime glass, borosilicate, or aluminosilicate glass, including chemically strengthened alkali aluminosilicate glass (such as Corning's material called Gorilla→glass). The thickness of the substrate can vary depending on the intended application and cost, and can be, for example, greater than about 0.1 mm, including from about 0.2 mm to about 5 mm, from about 0.3 mm to about 2 mm, or from about 0.5 mm to about 1.0 mm. The thickness of the metal oxide film can also vary from about 0.1 microns to about 50 microns, including from about 0.5 microns to about 20 microns and from about 1 micron to about 10 microns. Further, the metal oxide film is preferably substantially free of inert gas impurities (for example, argon, helium, or neon) as described above.

The metal oxide film can impart improved properties to the substrate. Therefore, by combining a relatively thick substrate material with a deposited thin metal oxide surface film, the resulting coated substrate will have the surface characteristics of the metal oxide film while also achieving the desired overall properties of the base substrate material. The significant difference between these coated substrates and the composite substrate (including the material of the multilayer discontinuous layer) is that there is no or no need for adhesion of the layers, which is often the location of delamination and failure of the composite substrate. As a specific embodiment, it is contemplated that the aluminum oxide film will provide improved scratch resistance, abrasion resistance, and/or hardness to the surface of the glass substrate disposed thereon. Other benefits of the coated substrate are also contemplated, depending on the thickness and nature of the alumina coating and the type and thickness of the glass, including, for example, improved modified optical properties, high bending and mechanical strength, and fracture toughness (also That is, the fracture resistance of the coated substrate containing cracks or scratches, the modulus, and the stain resistance (modified or modified lipophilicity or hydrophilicity). Other metal oxide films are expected to provide corresponding improvements or modifications to other or similar substrates, and such combinations are recognized by those skilled in the art.

The resulting coated substrate can be used in a wide variety of end use applications. As a specific example, a coated substrate including Al ₂ O ₃ disposed on a glass substrate can be used as a cover for various consumer electronic devices. The electronic device can be any known in the art, including a display or display element, such as a mobile or portable electronic device, including but not limited to, an electronic media player for music and/or video, such as an mp3 player, a mobile phone ( Mobile phone), personal digital assistant (PDA), pager, laptop, or electronic notebook or tablet. The cover may be attached to the display surface of the display element of the device or it may be placed in a separate protective layer or positioned above or above the top of the display element and if desired to be subsequently removed. The alumina coated surface of the coated substrate in this particular example is the front surface of the cover sheet, the exterior surface, which is in order to utilize the properties of the coating, such as scratch resistance, but may also be a side surface to improve resistance to breakage. Sex and cracks. The overall thickness of the cover may depend on various factors, such as the number of alumina layers and the size of the device, but is typically less than or equal to about 5 mm, such as less than or equal to about 3 mm and less than or equal to about 1 mm.

All publications described herein are hereby incorporated by reference.

Although the present invention has been shown and described with reference to the preferred embodiments of the present invention, it will be understood by those skilled in the art .

10‧‧‧System

12‧‧‧ peripheral bar

14‧‧‧metallization area

16‧‧‧Reaction zone

18‧‧‧ drum

20‧‧‧Substrate

22‧‧‧Magnetron

24‧‧‧Inert gas source

26‧‧‧ front gallery

27‧‧‧ pores

28‧‧‧Outer baffle

30‧‧‧Ion source

32‧‧‧ gas source

34‧‧‧Fence

36‧‧‧Differential pump

38‧‧‧ inner baffle

40‧‧‧Outer baffle

42‧‧‧ hollow cathode electron source

Claims (20)

A deposition system comprising: a metallization region comprising a sputtering source for generating metal atoms; a reaction region comprising an ion source for generating reactive ions; and a rotatable support on which at least one substrate can be disposed, the rotatable support configured to be The at least one substrate is alternately moved between the metallization zone and the reaction zone; and the movable aperture is positioned such that at least a portion of the metal ions pass through the aperture relative to the sputtering source. The deposition system of claim 1, wherein the movable aperture is disposed between the sputtering source and the rotatable support. The deposition system of claim 1, further comprising a fence, the sputtering source being at least partially encircled in the enclosure. The deposition system of claim 1, wherein the fence includes an opening for use as an outlet for metal ions generated from the sputtering source of the fence. The deposition system of claim 4, wherein the movable aperture is in the opening relative to the fence to receive at least a portion of the metal ions exiting the fence via the opening. The deposition system of claim 5, wherein the pore is substantially marked by the opening of the fence. The deposition system of claim 1, wherein the pore system is formed in the aperture plate. The deposition system of claim 1, wherein the sputtering source The system is configured to generate a flow of metal ions that exhibit an angular distribution relative to a central propagation axis. The deposition system of claim 8, wherein the pore system is configured to move along the central propagation axis. The deposition system of claim 1, wherein the pore system is configured to provide an aiming beam of the metal atom, characterized in that at least one position of the aperture is less than about 30 degrees of divergence angle with respect to the sputtering source. . The deposition system of claim 1, wherein the sputtering source comprises a magnetron. The deposition system of claim 1, wherein the ion source is configured to generate oxygen ions. A coated substrate comprising: a base substrate; and a metal oxide film disposed on a surface of the substrate, wherein the metal oxide film is substantially free of inert gas atoms. The coated substrate of claim 13, wherein the metal oxide film has a thickness of from about 0.1 to about 50 microns. The coated substrate of claim 13, wherein the metal oxide film is an aluminum oxide film, and wherein the base substrate is glass or plastic. An electronic device comprising a cover plate, wherein the cover plate comprises a coated substrate, and wherein the coated substrate comprises a base substrate and a metal oxide film disposed on a surface of the substrate. The electronic device of claim 16, wherein the metal oxide film is substantially free of inert gas atoms. The electronic device of claim 16, wherein the metal oxide film is an aluminum oxide film, and wherein the base substrate is glass or plastic. The electronic device of claim 16, wherein the electronic device comprises at least one display element having a display surface, and wherein the cover is fixed to the display surface. The electronic device of claim 16, wherein the electronic device comprises at least one display element having a display surface, and wherein the cover is tied to a removable protective layer on top of the display surface.