High-voltage, low-pressure plasma-enhanced atomic layer deposition

Abstract

An atomic layer deposition (ALD) method and a barrier film are disclosed. The ALD method involves placing a substrate close to an electrode coupled to a power source, exposing the substrate to an oxygen-containing or nitrogen-containing gas at 0.8 Torr or less, and applying a voltage of at least 700 volts to the electrode using the power source to induce a plasma state in the oxygen-containing or nitrogen-containing gas near the substrate. High-quality barrier films can be fabricated using this method.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 62 / 842039, filed May 2, 2019, entitled “HIGH VOLTAGE, LOW PRESSURE PLASMEAENHANCED ATOMIC LAYER DEPOSITION,” the entirety of which is incorporated herein by reference. Technical Field

[0003] This disclosure relates to barrier films, and more particularly to high-voltage, low-pressure plasma-enhanced atomic layer deposition methods for forming such films, as well as related products and equipment. Background Technology

[0004] Atomic layer deposition (ALD) can be used to deposit thin films for a variety of practical applications. One such application of ALD thin films is as barrier materials.

[0005] ALD is similar to traditional chemical vapor deposition (CVD) processes, but at the atomic level, its self-limiting growth on the substrate surface is different. ALD is a process that can produce extremely conformal and highly dense films and provide pinhole-free coverage. A complete ALD cycle is usually referred to as a combination of two half-reactions. A single ALD cycle typically involves four steps: (1) exposing the substrate to gaseous precursor molecules that react with the substrate surface or other existing molecules on that surface (“reaction sites”) – this is the first half-reaction; (2) removing any precursor molecules that are not chemically bonded to the surface; (3) introducing gaseous reactant molecules that react with the precursor molecules and form the desired molecules on the surface – this is the second half-reaction; and (4) removing any unreacted reactant molecules, and also removing any reaction byproducts, leaving only the desired molecules, such as metal oxides, on the surface.

[0006] Some materials may exhibit poor barrier properties. For example, SiO2 formed by ALD. x Moisture-proof layers typically do not have a moisture content of less than 0.5 g / m² / day. 2 Water vapor transmission rate (WVTR) of 5 × 10⁶ / day. It has been reported that sputtered SiO₂ can achieve water vapor transmission rate as low as 5 × 10⁶ / day. -2 g / m 2 / day WVTR. It has been reported that for films with thicknesses exceeding micrometers, plasma-initiated chemical vapor deposition of SiO2... x Capable of achieving 9×10 -2 g / m 2 / day WVTR. However, those SiO x / SiO2 films do not have a sufficiently low WVTR to act as a "super barrier".

[0007] There is a demand for alternative ALD processes and high-quality barrier films. Attached Figure Description

[0008] To facilitate identification of any particular element or behavior in the discussion, one or more of the most significant digits in the reference number refer to the figure number in which the element was first introduced.

[0009] Figure 1 This is a side view of an ALD device according to some implementations.

[0010] Figure 2 This is a flowchart illustrating a method for performing ALD according to some implementations.

[0011] Figure 3 This is a cross-sectional view of a substrate having a film according to some embodiments.

[0012] Figure 4 This is a cross-sectional view of a substrate having a film according to some embodiments.

[0013] Figure 5 This is a cross-sectional view of a substrate having a film according to some embodiments.

[0014] Figure 6 This is a cross-sectional view of a substrate having a film according to some embodiments.

[0015] Figure 7 This is a top view of an ALD device according to some implementation methods.

[0016] Figure 8 This is a top view of an ALD device according to some implementation methods.

[0017] Figure 9 These are a set of graphs depicting the stress and wet etching rate of films produced according to the examples disclosed herein.

[0018] Figure 10 These are a set of graphs depicting the stress and wet etching rate of films produced according to the examples disclosed herein. Detailed Implementation

[0019] The embodiments disclosed herein include ALD apparatus, barrier materials, and related methods. It has been found that, compared to barrier films deposited using conventional ALD processes, exposing the substrate to oxygen- or nitrogen-containing plasma at low pressure (e.g., 0.1 to 0.8 Torr) and high voltage significantly reduces water vapor and oxygen permeability, increases density, and reduces stress. Furthermore, it has been observed that the plasma exposure time can be shortened compared to conventional ALD processes. Therefore, the ALD barrier layers formed according to the embodiments disclosed herein exhibit superior barrier properties compared to conventional ALD barrier layers and can be produced with increased production volumes.

[0020] It was observed that when using low pressure and high voltage, a water vapor transmission rate of 10 can be achieved. -4 Or a barrier layer of an order of magnitude smaller. Additionally, the etch rate decreases, indicating an increase in film density. When SiO is deposited according to the embodiments disclosed herein... x At that time, SiO x Compared to conventionally deposited SiO x It is more chemically resistant and more abrasion-resistant. Moreover, using the embodiments disclosed herein, the polymer can be coated without pre-drying.

[0021] Low-pressure, high-voltage plasma can be achieved by operating the plasma generator at a high voltage (e.g., at least 700 volts) on one or more electrodes of the plasma generator near the substrate.

[0022] As used herein, the terms "electrode" and "multiple electrodes" specifically refer to the region of the electrode that itself generates plasma. Typically, the electrode is larger than the actual plasma-emitting region, but most of the region is protected by a "dark space shield" located close enough to the electrode to prevent plasma generation. This is typically used to prevent plasma generation on the side or rear surface of the electrode(s). Therefore, the term "electrode" refers only to the portion of the electrode that actually emits plasma, excluding any passive components such as the "dark space shield."

[0023] Generally, the term "substrate" refers to a base substrate material and any other materials or chemicals carried thereon (e.g., a base substrate material having one or more layers of film grown or partially grown thereon). For example, devices may be formed on or within the surface of a semiconductor substrate and are considered part of the "substrate" for the purposes of this disclosure. Unless otherwise expressly stated, when referring to the "substrate," the base semiconductor material and the devices and layers therein and carried thereon will be included in the "substrate."

[0024] Figure 1This is a side view of an ALD device 100 according to some embodiments. The ALD device 100 includes a reaction chamber 114, a base 106 within the reaction chamber 114, and a pressure control system 112 configured to control the pressure of an oxygen-containing or nitrogen-containing gas 108 (also referred to herein as a process gas—not to be confused with purge gas) within the reaction chamber 114. The base 106 is configured to hold a substrate 102 on the reaction chamber 114 while exposing the substrate 102 to the oxygen-containing or nitrogen-containing gas 108. The substrate 102 may include chemisorbed metal precursors chemisorbed thereon. The ALD device 100 also includes a plasma generator including a power supply 110 operatively coupled to an electrode 104. The electrode 104 is located close to the base 106 (e.g., such that the electrode-to-substrate distance between at least one electrode 104 and the substrate 102 is 5 cm or less). The plasma generator is configured to induce a plasma state in an oxygen- or nitrogen-containing gas 108, thereby generating some chemicals (e.g., free radical oxygen or nitrogen species) in the oxygen- or nitrogen-containing gas 108 that react with chemisorbed metal precursors on the substrate 102 to form oxides or nitrides (e.g., by “burning off” other ligands and atoms on the metal precursors).

[0025] ALD equipment 100 is configured to deposit a film (e.g., a moisture barrier, oxygen barrier, etc.) on substrate 102 for at least a portion of the ALD process. During a portion of the ALD process, pressure control system 112 is configured to maintain a relatively low pressure within reaction chamber 114, while power supply 110 is configured to maintain a relatively high voltage applied to oxygen-containing gas or nitrogen-containing gas 108. In some embodiments, pressure control system 112 may include a gas delivery system with a controllable pumping rate, wherein the pressure can be controlled by adjusting the airflow. In some embodiments, a feedback system, such as a variable throttle valve or variable flow valve, may be used to provide feedback to a pressure sensor configured to sense the pressure of gas 108. As a non-limiting example, pressure control system 112 may maintain the pressure within reaction chamber 114 at 0.8 Torr or lower, while power supply 110 maintains a voltage of at least 700 volts. Importantly, the power remains constant as the pressure is adjusted, thereby changing the voltage. The voltage change may be manual or automatic in response to pressure changes. In some embodiments, the pressure control system 112 may be configured to maintain the pressure of the oxygen-containing gas or nitrogen-containing gas 108 at 0.1 Torr to 0.8 Torr. In some embodiments, the pressure control system 112 may be configured to maintain the pressure of the oxygen-containing gas or nitrogen-containing gas 108 at 0.2 Torr to 0.7 Torr. In some embodiments, the pressure control system 112 may be configured to maintain the pressure of the oxygen-containing gas or nitrogen-containing gas 108 at 0.3 Torr to 0.4 Torr. In some embodiments, the pressure control system 112 may be configured to maintain the pressure of the oxygen-containing gas or nitrogen-containing gas 108 at a nominal value of 0.5 Torr.

[0026] In some embodiments, the oxygen-containing gas or nitrogen-containing gas 108 does not react with the metal precursor unless it is plasma-radicalized. Similarly, the oxygen-containing gas or nitrogen-containing gas 108 may also not react with the deposited metal (e.g., a chemisorbed metal precursor) on the substrate 102 and the base material of the substrate 102 (e.g., a polymer substrate) unless it is plasma-radicalized. In some embodiments, any portion of the film growth resulting from the reaction with non-radicalized species is less than ten percent (10%) of the total film. This can be measured by running the process without plasma and measuring the growth rate of any component (possibly a CVD component) and then running the process with plasma and measuring the total growth rate. By comparing the growth rates with and without plasma, the percentage of film produced by the reaction with non-radicalized species can be determined. In some embodiments, the oxygen-containing gas or nitrogen-containing gas 108 includes oxygen-containing gases (e.g., including air, O2, CO, CO2, NO, N2O, NO2, or mixtures thereof). In some embodiments, the oxygen-containing gas or nitrogen-containing gas 108 includes a nitrogen-containing gas (e.g., N2, NH3, N2:H2 mixtures, and mixtures thereof). In some embodiments, the oxygen-containing gas or nitrogen-containing gas 108 includes a mixture of oxygen-containing gas and nitrogen-containing gas.

[0027] In some embodiments, the gaseous metal precursor comprises an amino-based silicon precursor (e.g., comprising at least one nitrogen atom directly bonded to a silicon atom). In some embodiments, the amino-based silicon precursor is selected from bis(diethylamino)silane (BDEAS), ORTHRUS (from Air Liquide), tri(diethylamino)silane (TDMAS or 3DMAS), bis(tert-butylamino)silane (BTBAS), diisopropylaminosilane (DIPAS), bis(diisopropylaminodisilane) (BDIPADS), trimethylsilylamine (TSA), neopentyl silane, N(SiH3)3, tris(isopropylamino)silane (TIPAS), bis(ethylmethylamino)silane (BEMAS), and diisopropylaminotrichlorosilane (DIPATCS).

[0028] Examples of gaseous titanium precursors include titanium tetraisopropoxide (TTIP), TiCl4, and tetrakisdimethylamindotitatium (TDMAT). Examples of gaseous niobium precursors include (tert-butylimino)tris(diethylamino)niobium (TBTDEN), niobium ethoxide, (tert-butylimino)triethylmethylaminoniobium (TBTEMN), and pentamethylaminotantalum (PDMAT). Examples of tantalum precursors include analogs of the above-mentioned tantalum. Examples of hafnium include tetraethylmethylaminohafnium (TEMAH), tetraethylaminohafnium (TDEAH), and tetraethylmethylaminohafnium (TDMAH), and HyALD (from AirLiquide). Examples of zirconium precursors include analogs of the above-mentioned zirconium.

[0029] In some embodiments, electrode 104 includes a cathode and an anode. In some embodiments, a negative voltage is applied to plasma electrode 104 (e.g., the electrode 104 closest to substrate 102), while another electrode 104 remains grounded (e.g., zero volts). The reaction chamber may also be grounded such that random surfaces within the reaction chamber can serve as effective anodes, with only one electrode 104. In some embodiments, at least one of the electrodes 104 is separated from substrate 102 by 5 cm (5 cm) or less (e.g., electrode 104 is in contact with oxygen-containing gas or nitrogen-containing gas 108 and faces the surface of substrate 102 to be coated). In some embodiments, at least one of the electrodes 104 is separated from substrate 102 by 0.1 cm to 5 cm, or 0.2 cm (0.2 cm) to 2 cm (2 cm). In some embodiments, at least one of the electrodes 104 is separated from substrate 102 by 0.3 cm (0.3 cm) to 2 cm (2 cm). The spacing, pressure, voltage, and power are selected such that the plasma completely occupies the space between substrate 102 and the electrode 104 facing the surface of substrate to be coated. This can be determined by optical examination of the plasma glow. Other methods known in the art for determining the plasma range can also be used.

[0030] Figure 2 This is a flowchart illustrating a method 200 for performing ALD according to some embodiments. Also refer to... Figure 1 and Figure 2 Method 200 includes 202 placing a substrate 102 near an electrode 104 operatively coupled to a power source 110.

[0031] Method 200 further includes 204 exposing substrate 102 to an oxygen-containing gas or nitrogen-containing gas 108 at or below 0.8 Torr. In some embodiments, exposing substrate 102 to an oxygen-containing gas or nitrogen-containing gas 108 at or below 0.8 Torr includes introducing a precursor gas into substrate 102 at a nominal value of 0.1 Torr.

[0032] In some embodiments, exposing the substrate 102 to an oxygen-containing gas or a nitrogen-containing gas 108 at 204 includes exposing the substrate 102 to the oxygen-containing gas or nitrogen-containing gas 108 at a first pressure of 0.8 Torr or less during the formation of a first film on the substrate 102, and exposing the substrate 102 to the oxygen-containing gas or nitrogen-containing gas 108 at a second pressure of 0.8 Torr or less during the formation of a second film on the substrate 102. The first film has a first type of stress, and the second film has a second type of stress different from the first type of stress. In some embodiments, the second type of stress at least partially offsets the first type of stress. As a non-limiting example, the first type of stress may include tensile stress, and the second type of stress may include compressive stress. Also as a non-limiting example, the first type of stress may include compressive stress, and the second type of stress may include tensile stress.

[0033] Method 200 further includes 206 applying a voltage of 700 volts or more (e.g., 700 volts to 1500 volts) to electrode 104 using power supply 110 to induce a plasma state in oxygen-containing or nitrogen-containing gas 108 near substrate 102. In some embodiments, 206 applying a voltage to at least one electrode 104 includes applying a pulsed or continuous direct current (DC) voltage or alternating current (AC) voltage at a frequency of less than 500 kHz (including less than 100 kHz). In some embodiments, high-power pulses with a relatively low duty cycle (e.g., exceeding 20 W / cmW), such as those used in high-power pulsed magnetron sputtering (HIPIMS), can be used to provide high voltages, provided the average power remains constant.

[0034] In some embodiments, method 200 further includes 208 exposing substrate 102 (e.g., after exposure 204) to a gaseous metal precursor and forming a metal oxide, metal nitride, or a combination thereof on substrate 102. The exposures 204 and 208 and the application 206 action can be repeated to grow a metal oxide film, a metal nitride film, or a combination thereof on substrate 102. In some embodiments, exposing substrate 102 204 to an oxygen-containing or nitrogen-containing gas 108 occurs in a plasma region, and subsequently exposing substrate 208 to a gaseous metal precursor occurs in a precursor region. In some such embodiments, repeating the exposures 204 and 208 and the application 206 action includes repeatedly transporting substrate 102 from the plasma region to the precursor region. In some embodiments, exposing substrate 102 208 to a gaseous metal precursor occurs at a higher pressure than exposing substrate 102 204 to an oxygen-containing or nitrogen-containing gas 108.

[0035] It should be understood that Method 200 spans a single ALD cycle. The steps of Method 200 are typically repeated multiple times during film growth. Studies have found that the stress of the resulting film can be controlled by varying the voltage and pressure while keeping the power supply constant. Therefore, this paper considers a method for adjusting film stress using Method 200.

[0036] For example, a method for regulating stress in a thin film includes providing a plasma-enabled atomic layer deposition (ALD) reactor with a DC power supply or a relatively low-frequency AC power supply (non-RF frequency), and placing a substrate close to at least one electrode coupled to the power supply of the ALD reactor. Next, the substrate is exposed to an oxygen-containing or nitrogen-containing gas at a first pressure of 0.8 Torr or less, and a first voltage of at least 700 volts is applied to at least one electrode using the power supply to induce a plasma state in the oxygen-containing or nitrogen-containing gas near the substrate. The substrate is then exposed to a gaseous metal precursor, and a metal oxide, metal nitride, or a combination thereof is formed on the substrate. The exposure is repeated to grow a metal oxide film, a metal nitride film, or a combination thereof on the substrate to form a first film with a first type of stress. Next, the first pressure is adjusted to a second pressure of 0.8 Torr or less, and the first voltage is adjusted to a second voltage of at least 700 volts, wherein the first voltage and the second voltage are applied over time with the same power or with the same average power over time. The substrate is exposed to an oxygen- or nitrogen-containing gas at a second pressure, and a second voltage is applied to at least one electrode using a DC power supply to induce a plasma state in the oxygen- or nitrogen-containing gas near the substrate. The substrate is then exposed to a gaseous metal precursor, and a metal oxide, metal nitride, or a combination thereof is formed on the substrate. The exposure process is repeated to grow a metal oxide film, a metal nitride film, or a combination thereof on the substrate to form a second film with a second type of stress, including a final film of the first and second films having a different stress, type, or both than the first film.

[0037] One advantage of the above method is that the final film can have low stress, such as neutral stress, tensile stress less than 200 MPa, less than 150 MPa, or less than 100 MPa, or compressive stress less than -200 MPa, less than -150 MPa, or less than -100 MPa. In contrast, conventional ALD typically produces films with high tensile stress.

[0038] Another advantage of the method described above is that the resulting films tend to be denser than conventional ALD films. For example, the final film (and each of one or more films) can have a density greater than 90%, 95%, 96%, 97%, 98%, or 99% of the theoretical bulk density. The theoretical bulk density is the ideal density of a material. For crystalline materials, this is the ideal crystal density with atomic separation found in natural crystals. For materials that are typically amorphous, such as amorphous SiO2, the theoretical bulk density refers to the bulk density of thermally grown SiO2 on silicon or "fused silica," a synthetically produced amorphous SiO2. Surprisingly, both low stress and high density can be achieved using the method disclosed herein. This is something that no other thin film deposition technique can achieve.

[0039] In addition, for relatively thick films, such as single films with a thickness of at least 10 nm, at least 20 nm, at least 50 nm, at least 100 nm, at least 150 nm or at least 200 nm, the advantages of low stress and high density can be maintained.

[0040] The final film may include multiple films. It should be understood that when it is not desired to adjust the stress of the first film, such as when the first film is produced under neutral stress, or when the underlying substrate is under stress and the first film is sufficient to neutralize the stress of the substrate, the final film may contain only a single film.

[0041] It should be understood that the same or different precursors containing gaseous metals can be used for different films of the final thin film.

[0042] Figure 3 This is a cross-sectional view of a substrate 300 having a film according to some embodiments. The substrate 300 having a film includes a substrate 302 and a film 304. Figure 1 ALD device 100, according to Figure 2 Method 200 forms film 304. In some embodiments, substrate 302 comprises a flexible polymer film having a glass transition temperature of 100°C or lower. In some embodiments, film 304 has a refractive index of 1.45 or greater, for example, 1.45 to 1.55 at 633 nm, indicating high-density SiO2. xFilm. In some embodiments, substrate 302 is rigid. In some embodiments, substrate 302 includes an organic light-emitting diode (OLED) display, an optical device, an optical coating, or an optical interference filter. In some embodiments, substrate 302 includes an illumination panel. In some embodiments, substrate 302 includes a substrate for an electronic device (e.g., a printed circuit board carrying one or more circuit components, such as a semiconductor package, a semiconductor device substrate, etc.). In some embodiments, substrate 302 includes semiconductor materials such as silicon, gallium arsenide, III-V semiconductor materials, II-VI semiconductor materials, silicon-on-insulator (SOI) substrates, silicon-on-glass substrates, silicon-on-sapphire (SAS) substrates, other semiconductor materials, or combinations thereof. In some embodiments, substrate 302 may include one or more semiconductor devices formed therein or on it.

[0043] In some embodiments, film 304 may have a thickness of 500 angstroms or less. In some embodiments, film 304 includes a barrier layer (e.g., a moisture barrier, an oxygen barrier, etc.) formed on substrate 302. Advantageously, using the methods disclosed herein, the barrier layer can be formed at 150°C or lower (e.g., 120°C or lower and 100°C or lower) by alternately exposing substrate 302 to a gaseous silicon-containing precursor and a low-pressure oxygen plasma (with a pressure of 0.1 Torr to 0.8 Torr). This can allow the growth of thin films on temperature-sensitive substrates, such as flexible polymer substrates with relatively low melting points. As a specific non-limiting example, film 304 may include silicon and oxygen (e.g., silicates, SiO2). x Where "x" is a value ranging from 1 to 2 (e.g., 1.6, 1.8, etc.) for a thin film barrier layer. In some embodiments, film 304 has a 3×102 -3 grams per square meter per day (g / m²) 2 / day) or less, 5×10 -5 g / m 2 / day or less, or 1×10 -6 g / m 2 / day or less of water vapor transmission rate. In some embodiments, the membrane 304 has a thickness greater than 300 nm and has 3 × 10 -3 g / m 2 / day or less, 5×10 -5 g / m 2 / day or less or 1×10 -6 g / m 2 / day or less of water vapor throughput. In some embodiments, the membrane 304 has a thickness greater than 300 nm and has a density of 5 × 10⁻⁶ nm. -3 cm 3 / m 2 / day or less of oxygen vapor permeability. In some embodiments, membrane 304 has a refractive index of 1.45 or greater at 633 nm. The higher the refractive index, the denser membrane 304. Increased density indicates that membrane 304 has lower porosity, which corresponds to reduced WVTR and oxygen permeability. For example, membrane 304 may have a density of at least 90% of the theoretical bulk density. In addition, membrane 304 may have low stress.

[0044] In some embodiments, film 304 may be formed directly on substrate 302. However, in some embodiments, film 304 may be formed directly on one or more intermediate layers. Figure 5 An example implementation of this is shown. In some implementations, the substrate 302 may not be cleaned or pretreated before forming the film 304.

[0045] In some embodiments, film 304 includes a barrier layer formed on substrate 302. The barrier layer comprises SiO2 formed at 150°C or lower by alternately exposing substrate 302 to a gaseous silicon-containing precursor and a low-pressure, high-voltage oxygen plasma. x Thin film. SiO x The film has a thickness of less than 500 angstroms and has a density of 3 × 10⁻⁶. -3 g / m 2 / day or less, 5×10 -5 g / m 2 / day or less or 1×10 -6 g / m 2 / day or less of water vapor transmission rate, wherein low-pressure oxygen plasma includes oxygen plasma of 0.8 Torr or less.

[0046] In some embodiments, film 304 includes a barrier layer formed on substrate 302. This barrier layer comprises SiO₂ formed at 150°C or lower by alternately exposing substrate 302 to a gaseous silicon-containing precursor and a low-pressure, high-voltage oxygen plasma. x Thin film. SiO x The thin film has a thickness greater than 300 nm and has a density of 3 × 10⁻⁶ nm. -3 g / m 2 / day or less, 5×10 -5 g / m 2 / day or less or 1×10 -6 g / m 2 / day or less of water vapor transmission rate.

[0047] In some embodiments, membrane 304 includes reaction products, which include products of exposing adsorbed silicon-containing precursors to a low-pressure oxygen plasma at a pressure of 0.1 Torr to 0.8 Torr. The adsorbed silicon-containing precursors are adsorbed onto substrate 302 at a temperature of 150°C or lower.

[0048] Figure 4 This is a cross-sectional view of a substrate 400 having a film according to some embodiments. The substrate 400 having a film includes components similar to... Figure 3 The substrate 402 and film 404 are substrate 302 and film 304, respectively. However, the substrate 400 having the film includes an organic smoothing layer 406. The organic smoothing layer 406 is configured to compensate for any defects on the surface of the substrate 402.

[0049] Figure 5 This is a cross-sectional view of a substrate 500 having a film according to some embodiments. The substrate 500 having a film may be similar to... Figure 3 The substrate 300 with the film and / or Figure 4 The substrate 400 has a film. The substrate 500 with a film includes a substrate 502 and a film 504. The substrate 502 is encapsulated within the film 504.

[0050] Figure 6 This is a cross-sectional view of a substrate 600 having a film according to some embodiments. According to the embodiments disclosed herein, the substrate 600 having a film includes a substrate 602 and a film 604 formed thereon. The substrate 602 and the film 604 may be similar to... Figure 3 membrane 304, Figure 4 The membrane 404 and Figure 5 The film 504. In some embodiments, the film 604 may include multiple layers. One or more of these layers can be used to expose the substrate 602 to a metal precursor and to expose the substrate 602 to an oxygen-containing gas or a nitrogen-containing gas 108 in a paired manner. Figure 1 (Formed. For example,) Figure 6 A film 604 having four layers is shown, namely layer 606, layer 608, layer 610, and layer 612. Within the scope of this disclosure, film 604 may comprise any number of layers, greater than or equal to two.

[0051] As discussed above, it has been found that by varying the pressure of the oxygen-containing or nitrogen-containing gas 108 within the range of 0.1 Torr to 0.8 Torr, and correspondingly varying the voltage, while maintaining a constant power supply, the stress of the resulting film 604 deposited on the substrate 602 can be controlled. As a result, the stress in each of the layers 606, 608, 610, 612 can be controlled to eliminate stress in the underlying or overlying material. For example, the stress in layer 606 can be of a first type, and the stress in layer 608 can be of a second type, different from the first type. As a specific non-limiting example, the second type of stress may include tensile stress, while the first type of stress may include compressive stress. As another specific non-limiting example, the second type of stress may include compressive stress, while the first type of stress may include tensile stress. In some such embodiments, the pressure of the oxygen-containing or nitrogen-containing gas 108 used to form each of the layers 606, 608, 610, 612 may be selected to control the stress in layers 606, 608, 610, 612 to be neutral.

[0052] In some embodiments, one or more of layers 606, 608, 610, and 612 may include the same material as one or more of layers 606, 608, 610, and 612. As a non-limiting example, each of layers 606, 608, 610, and 612 may include the same material. In some embodiments, one or more of layers 606, 608, 610, and 612 may include a material different from one or more of the other layers 606, 608, 610, and 612. As a non-limiting example, one of layers 606, 608, 610, and 612 may include SiO2. x And another of layers 606, 608, 610, and 612 may include Nb y O z , where “y” is close to 2 and “z” ranges from 1 to 5.

[0053] In some embodiments, substrate 602 may have a different coefficient of thermal expansion (CTE) than film 604. Pressure can be selected to induce internal stress at elevated deposition temperatures such that the CTEs of substrate 602 and film 604 are balanced when substrate 600 with film is cooled. This embodiment extends to embodiments where the thin film is only a single layer. In other words, even in the case of depositing a single-layer film on the substrate, pressure can be selected to balance the CTEs of the substrate and film upon cooling.

[0054] Figure 7 This is a top view of an ALD device 700 according to some embodiments. The ALD device 700 includes a plasma region 704, a precursor region 706, and a transport means configured to transport a substrate between the plasma region 704 and the precursor region 706. The plasma region 704 may include the components described above. Figure 1The ALD device 100 under discussion. Specifically, the plasma region 704 includes a structure similar to... Figure 1 The oxygen-containing gas or nitrogen-containing gas 108 and the oxygen-containing gas or nitrogen-containing gas 710 are respectively. The pressure of the oxygen-containing gas or nitrogen-containing gas 710 at the plasma region 704 and the power of the plasma generator can be controlled according to the embodiments disclosed herein. For example, the pressure can be maintained in the range of 0.1 Torr to 0.8 Torr, and the surface power density can be maintained greater than or equal to 1 W / cm². 2 .

[0055] Except that a plasma generator cannot be used, precursor region 706 may be similar to plasma region 704. Furthermore, a pressure control system may or may not be used. Precursor region 706 is configured to expose the substrate to gaseous metal precursor 712. In some embodiments, the pressure of the gaseous metal precursor 712 within precursor region 706 is the same as the pressure of the oxygen-containing gas or nitrogen-containing gas 710 within plasma region 704. In some embodiments, the pressure of the gaseous metal precursor 712 in precursor region 706 is different from the pressure of the oxygen-containing gas or nitrogen-containing gas 710 in plasma region 704.

[0056] Figure 7 The transport device of the ALD apparatus 700 includes a rotating member 702 configured to rotate about a pivot 708. One or more substrates to be treated may be coupled to a surface 714 of the rotating member 702 (e.g., using vacuum-induced suction, electromagnets, jigs, gravity, etc.). As the rotating member 702 rotates about the pivot 708, one or more substrates may alternate between a plasma region 704 and a precursor region 706. In some embodiments, a purge gas 716 may be located between the plasma region 704 and the precursor region 706 to remove any residual chemicals from the substrate as it moves between the plasma region 704 and the precursor region 706 with the rotation of the rotating member 702.

[0057] In some embodiments, the rotational speed of the rotating member 702 can be controlled to provide the required amount of time for the substrate to be exposed to the oxygen- or nitrogen-containing gas 710 of the plasma region 704 and the gaseous metal precursor 712 of the precursor region 706.

[0058] Figure 8 This is a top view of an ALD device 800 according to some embodiments. The ALD device 800 includes a plasma region 802, a precursor region 804, and a delivery means configured to deliver one or more substrates between the plasma region 802 and the precursor region 804. A purge gas 810 may be located between the plasma region 802 and the precursor region 804. The plasma region 802 and the precursor region 804 may be respectively similar to... Figure 7The ALD device 700 has a plasma region 704 and a precursor region 706. In other words, the plasma region 802 is configured to expose the substrate to an oxygen-containing gas or nitrogen-containing gas 806 similar to an oxygen-containing gas or nitrogen-containing gas 710, and the precursor region 804 is configured to expose the substrate to a gaseous metal precursor 808 similar to a gaseous metal precursor 712.

[0059] Figure 8 The transport device of the ALD apparatus 800 includes a transport system 812 configured to transport one or more substrates between a plasma region 802 and a precursor region 804. One or more substrates to be processed may be coupled to the transport system 812 (e.g., using vacuum-induced suction, electromagnets, jigs, gravity, etc.) for transport between the plasma region 802 and the precursor region 804. In some embodiments, the substrate itself may be the transport device (e.g., as in roll-to-roll processing).

[0060] With the benefit of this disclosure, those skilled in the art will understand that a variety of ALD reactors can be used to perform the methods disclosed herein, such as at least some of the reactors disclosed in U.S. Patent No. 8,187,679 (the entire contents of which are incorporated herein).

[0061] Example 1

[0062] Figure 9 This is a set of graphs 900 showing the stress and wet etching rate of the film produced according to a series of experiments. The film was deposited using a substrate maintained at 100°C. The substrate was a silicon wafer. DIPAS was used as the precursor gas at room temperature, utilizing vapor evacuation and 0.8 mm orifice confinement. Similar to... Figure 7 The ALD device 700 is a rotating ALD device used in a space ALD at a rotation speed of 100 revolutions per minute (RPM, corresponding to 100 ALD cycles per minute). All operating power was maintained at 300 watts. The total film thickness deposited was 180 nanometers (nm). The gap between the electrode and the substrate was 1.2 cm.

[0063] The pressure was varied between 0.4 Torr and 1.2 Torr to illustrate the effect of pressure on stress and wet etching rate. Although the power remained constant at 300 watts, the current and voltage supplied by the plasma generator varied with pressure because changes in the pressure of the oxygen- or nitrogen-containing gas (process gas) are equivalent to changes in the impedance of the oxygen- or nitrogen-containing gas. As a result, lower pressure corresponded to higher voltage and lower current compared to higher pressure, which corresponded to lower voltage and higher current. The test results are included in Table 1 below.

[0064] Table 1

[0065] Pressure (or stress) Electric current (amperes) Voltage Stress (MPa) Wet etching rate (nm / min) 1.2 0.5 600 280 33 1.0 0.5 640 240 30 0.8 0.4 700 220 18 0.7 0.4 730 90 14 0.6 0.4 770 40 14 0.5 0.4 800 20 13 0.4 0.3 910 -20 12

[0066] Wet etching rates were measured at room temperature using 1% pure HF in water. Furthermore, the positive stress values ​​in the table correspond to tensile stress, while the negative stress values ​​correspond to compressive stress.

[0067] Graph 900 includes stress curve 902, which shows stress as a function of pressure. Stress curve 902 shows that tensile stress increases significantly at 0.8 Torr. Stress curve 902 also shows that the stress of the deposited film can be controlled by selecting appropriate pressures for oxygen- or nitrogen-containing gases (e.g., by using layers of film to eliminate stress or selecting one or more layers of neutral stress).

[0068] Graph 900 also includes a wet etching rate curve 904, which shows the wet etching rate as a function of pressure. As shown in wet etching rate curve 904, the wet etching rate increases significantly between 0.8 Torr and 1 Torr. As a result, higher film densities are produced when the pressure of the oxygen-containing or nitrogen-containing gas is 0.8 Torr or below.

[0069] Additional runs were performed at 1.2 Torr, where the plasma generator operated at 0.5 Amps and 600 V, but the rotational speed was halved to 50 RPM, effectively doubling the plasma exposure time in the plasma region. A stress of 120 MPa and a wet etching rate of 24 nm / min were measured. Therefore, even with the plasma exposure time doubled in the higher pressure (1.2 Torr) plasma region, the film density was still not as high as that achieved using lower pressure (e.g., 0.1 Torr to 0.8 Torr) plasma regions. Even at 1.2 Torr pressure, with the power increased to 500 W (0.74 Amps and 680 V), a wet etching rate of 16 nm / min was obtained (higher than the 14 nm / min wet etching rate achieved at 0.7 Torr in the table), and a stress of 160 MPa.

[0070] Example 2

[0071] Figure 10 This is a set of graphs 1000 showing the stress and wet etching rate of the film produced according to another set of experiments. The film was deposited using a silicon wafer substrate maintained at 80°C. BTBAS was a precursor gas at 50°C and delivered using vapor traction. Similar to... Figure 7 A 700 rotary ALD device was used, operating at 150 RPM (corresponding to 150 ALD cycles per minute), utilizing a spatial ALD. All operating power was maintained at 500 watts. The total deposited film thickness was 300 nanometers (nm). The gap between the substrate and the electrode was 1.2 cm.

[0072] The pressure was varied between 0.4 Torr and 1.4 Torr to illustrate the effect of pressure on stress and wet etching rate. Although the power remained constant at 500 watts, the current and voltage supplied by the plasma generator varied with pressure because changes in the pressure of the oxygen- or nitrogen-containing gas are equivalent to changes in the impedance of the oxygen- or nitrogen-containing gas. As a result, lower pressure corresponded to higher voltage and lower current compared to higher pressure, which corresponded to lower voltage and higher current. The test results are included in Table 2 below.

[0073] Table 2

[0074] Pressure (or stress) Electric current (amperes) Voltage Stress (MPa) Wet etching rate (nm / min) 1.4 0.8 630 260 56 1.2 0.8 660 220 44 1.0 0.7 690 280 34 0.8 0.7 750 140 27 0.7 0.6 780 170 26 0.6 0.6 830 95 20 0.5 0.6 870 40 16 0.4 0.5 980 -40 13

[0075] Wet etching rates were measured at room temperature using 1% anhydrous HF in water. Furthermore, the positive stress values ​​in the table correspond to tensile stress, while the negative stress values ​​correspond to compressive stress.

[0076] Graph 1000 includes stress curve 1002, which shows stress as a function of pressure. Stress curve 1002 shows that tensile stress increases significantly above 0.8 Torr. Stress curve 1002 also shows that the stress of the deposited film can be controlled by selecting appropriate pressures for oxygen- or nitrogen-containing gases (e.g., by using film layers to eliminate stress or selecting one or more layers of neutral stress).

[0077] Graph 1000 also includes a wet etching rate curve 1004, which shows the wet etching rate as a function of pressure. As shown in wet etching rate curve 1004, the rate of change of the wet etching rate increases significantly above 0.8 Torr. As a result, higher film densities are produced when the pressure of the oxygen-containing or nitrogen-containing gas is 0.8 Torr or below.

[0078] Example 3

[0079] Additional experiments were conducted to further understand the embodiments disclosed herein. All experiments in this embodiment used vapor suction as the delivery mechanism. Table 3 below shows the SiO₂... x How the stress on the membrane adapts relatively to changes in plasma exposure time.

[0080] Table 3

[0081]

[0082] As shown in Table 3, by changing the rotational speed of the ALD device from 60 RPM to 150 RPM, the stress measured in the SiO2 film changed by only 10 MPa.

[0083] As shown in Table 4 below, the stress changes only slightly when there is a current difference of 3.4 times (the total power change is greater than 4 times).

[0084] Table 4

[0085] Precursor Cover layer Temperature (°C) Speed ​​(RPM) Stress (Torr) Electric current (amperes) Stress (MPa) BTBAS TiO2 120 120 1.1 1.5 290 BTBAS TiO2 120 120 1.1 0.5 390 BTBAS TiO2 120 120 1.1 1.7 270

[0086] As shown in Table 5 below, pressure is a key variable in the process. It should be noted that voltage is also a key variable, as it varies with pressure to maintain constant power during pressure changes.

[0087] Table 5

[0088] pressure Cover layer Temperature (°C) Speed ​​(RPM) Pressure (or stress) Electric current (amperes) Stress (MPa) BTBAS TiO2 120 120 1.1 1.5 240 BTBAS TiO2 120 120 0.7 1.5 160 BTBAS <![CDATA[TiO2]]> 120 120 0.5 1.0 50

[0089] Table 6 below shows another example of how stress changes only slightly with variations in plasma exposure time when operating at low pressure and constant power.

[0090] Table 6

[0091] Precursor Cover layer Temperature (°C) Speed ​​(RPM) Pressure (or stress) Electric current (amperes) Stress (MPa) BTBAS <![CDATA[TiO2]]> 120 120 0.3 0.5 60 BTBAS <![CDATA[TiO2]]> 120 150 0.5 1 30 BTBAS <![CDATA[TiO2]]> 120 180 0.5 1 40

[0092] A control experiment was conducted to test the wet etching rate of the SiO2 film. In the control experiment, a BTBAS precursor was used at a temperature of 100°C, a speed of 120 RPM, a pressure of 1 Torr, a current of 1 Ampere, and a voltage of 475 V. Therefore, a wet etching rate of 650 Å / min was measured. Four additional experiments were also conducted within the pressure range (0.1 Torr to 0.8 Torr) of the embodiments of this disclosure, and are summarized in Table 7.

[0093] Table 7

[0094] Precursor Temperature (°C) Speed ​​(RPM) Pressure (or stress) Electric current (amperes) Wet etching rate (A / min) BTBAS 120 60 0.5 1 140 BTBAS 120 60 0.45 1 140 BTBAS 120 60 0.4 1 140 BTBAS 120 60 0.35 1 150

[0095] As shown in Table 7, a pressure reduction below 0.8 Torr does not significantly regulate density.

[0096] Table 8 shows that maintaining a high voltage is important.

[0097] Table 8

[0098]

[0099] In Table 8, a wet etch rate >270 indicates that all films were etched, so the actual wet etch rate cannot be determined.

[0100] Example 4

[0101] Tables 3-8 are all based on SiO2 films. Table 9 shows TiO2 prepared using TTIP as a gaseous metal precursor and O2 as an oxygen-containing gas for plasma.x Experimental results of the membrane.

[0102] Table 9

[0103] Precursor Temperature (°C) Speed ​​(RPM) Pressure (or stress) Electric current (amperes) Voltage (volts) Stress (MPa) TTIP 100 120 1.0 0.7 440 440 TTIP 100 120 0.4 0.7 920 40

[0104] Table 9 shows that the stress generated during operation within the pressure range of this disclosure (0.1 Torr to 0.8 Torr) is much smaller.

[0105] Example 5

[0106] Table 10 shows SiO₂ deposition using precursors other than BTBA. x The stress on the film and the wet etching rate.

[0107] Table 10

[0108]

[0109]

[0110] As can be seen from Table 10, SiO₂ deposited using each of the precursors in Table 10 x The film exhibits good stress and wet etching rate.

[0111] Example 6

[0112] Experiments were conducted at room temperature using a diisopropylaminosilane (DIPAS) precursor at a substrate temperature of 100°C. The precursor was passively delivered by evaporation through a confining orifice with a diameter of 0.8 mm. For all runs, the power was kept constant at approximately 300 W, with an electrode surface area of ​​approximately 135 cm² (resulting in a surface power density of 2.22 W / cm²). Pure oxygen was used as both plasma and purge gas, with the flow rate varied to alter the chamber pressure. The substrate used was DuPont Teijin Mellinex ST-504 with a thickness of 125 μm. No cleaning or pretreatment of the substrate was performed prior to ALD runs. Water vapor transmission rate (WVTR) was measured using an Illinois Instruments Model 7001 Water VaporPermeation Analyzer under test conditions of 38°C and 90% relative humidity. The WVTR of the uncoated substrate was approximately 5 g / m². 2 / day. The ALD coating thickness was determined by measuring the silicon witness coupon using a Rudolph EL III ellipsometry.

[0113] Experiment 1: An O2 flow rate of 420 SCCM resulted in a chamber pressure of 0.5 Torr. The average plasma voltage was approximately 810 V. Rotation at 100 RPM for 485 revolutions produced a thickness of 450 angstroms. The measured WVTR of this sample was below the instrument's specified sensitivity, i.e., 0.003 g / m³. 2 / sky.

[0114] Experiment 2: An O2 flow rate of 1600 SCCM resulted in a chamber pressure of 1.2 Torr. The average plasma voltage was approximately 580 V. Rotation at 100 RPM for 485 revolutions produced... The thickness of the sample. The WVTR measurement value of this sample is 4.4 g / m. 2 / sky.

[0115] Experiment 3: An O2 flow rate of 1600 SCCM resulted in a chamber pressure of 1.2 Torr. The average plasma voltage was approximately 580 V. Rotation at 50 RPM for 485 revolutions produced... The thickness of the sample. The WVTR measurement value of this sample is 1.55 g / m. 2 / sky.

[0116] in conclusion

[0117] Those skilled in the art will understand that many changes can be made to the embodiments disclosed herein without departing from the scope of this disclosure. Therefore, the scope of the invention should be defined only by the claims.

Claims

1. A method of performing atomic layer deposition, the method comprising the steps of: positioning a substrate proximate to an electrode such that the electrode and the substrate are separated to leave a gap therebetween; exposing the substrate to a process gas at a pressure of 0.8 Torr or less while applying a voltage of at least 700 volts to the electrode at a frequency of less than 100 kHz to induce a plasma in the process gas that occupies the entire gap, the process gas being selected from the group consisting of an oxygen-containing gas, a nitrogen-containing gas, and mixtures thereof; and exposing the substrate to a gaseous metal-containing precursor.

2. The method of claim 1, wherein the pressure is 0.1 Torr.

3. The method of claim 1, wherein the voltage applied to the electrode is a constant or pulsed DC voltage.

4. The method of claim 1, wherein the voltage applied to the electrode is an AC voltage.

5. The method of any one of claims 1-4, wherein after exposing the substrate to a gaseous metal-containing precursor, further comprising the steps of: (a) exposing the substrate to a process gas at a first pressure of 0.8 Torr or less while applying a voltage of at least 700 volts to the electrode at a frequency of less than 500 kHz to form a first film having a first type of stress on the substrate; (b) after step (a), again exposing the substrate to the metal-containing precursor; (c) during a period of time between and including step (a) and step (d), adjusting the pressure of the process gas between the first pressure and a second pressure that is also 0.8 Torr or less but is different than the first pressure; and (d) after step (b), exposing the substrate to a process gas at the second pressure while applying a voltage of at least 700 volts to the electrode at a frequency of less than 500 kHz to form a second film having a second type of stress on the first film that is different than the first type of stress.

6. The method of claim 5, wherein the second pressure is selected such that the second type of stress at least partially cancels the first type of stress.

7. The method of claim 6, wherein the first type of stress comprises a tensile stress and the second type of stress comprises a compressive stress.

8. The method of claim 6, wherein the first type of stress comprises a compressive stress and the second type of stress comprises a tensile stress.

9. The method of any one of claims 1-4, further comprising: alternating the steps of exposing the substrate to the process gas and exposing the substrate to the gaseous metal-containing precursor a plurality of times to grow a metal oxide film, a metal nitride film, or a combination thereof on the substrate.

10. The method of claim 9, wherein subsequently exposing the substrate to the gaseous metal-containing precursor occurs at a higher pressure than exposing the substrate to the process gas.

11. The method of claim 9, wherein exposing the substrate to the process gas occurs in a plasma zone and subsequently exposing the substrate to the gaseous metal-containing precursor occurs in a precursor zone separate from the plasma zone, and wherein the repeating exposing acts comprise repeatedly transporting the substrate from the plasma zone to the precursor zone.

12. The method of claim 1, wherein the gaseous metal-containing precursor does not react with the process gas when the process gas is not in a plasma state.

13. The method of claim 1, wherein the gaseous metal-containing precursor comprises an amino-based silicon precursor.

14. The method of claim 13, wherein the amino-based silicon precursor comprises at least one nitrogen atom directly bonded to a silicon atom.

15. The method of claim 13, wherein the amino-based silicon precursor is selected from the group consisting of bisdiethylaminosilane (BDEAS), tridiethylaminosilane (TDMAS or 3DMAS), bis-tert-butylaminosilane (BTBAS), diisopropylaminosilane (DIPAS), bisdiisopropylaminodisilane (BDIPADS), trisilylamine (TSA), N(SiH3)3, tris(isopropylamino)silane (TIPAS), bis(ethylmethylaminosilane) (BEMAS), and diisopropylaminotrichlorosilane (DIPATCS).

16. The method of claim 3, wherein the constant or pulsed DC voltage is between 700 volts and 1500 volts.

17. The method of claim 1, wherein the electrode is separated from the substrate by 5 cm or less, and the process gas is introduced between the electrode and the substrate.

18. The method of claim 1, wherein the voltage is applied at a constant power over time or a constant average power over time.

19. The method of claim 1, wherein the substrate does not react with the process gas when the process gas is not in a plasma state.

20. The method of claim 1, wherein the process gas comprises air, O2, CO, CO2, NO, N2O, NO2, and mixtures of the foregoing.

21. The method of claim 1, wherein the process gas comprises N2, NH3, N2:H2 mixtures, and mixtures of the foregoing.

22. The method of any of claims 1-4, wherein the method is performed at a temperature of less than 150 °C, and the substrate is a temperature sensitive substrate.

23. The method of any of claims 1-4, wherein the substrate is not cleaned or pretreated.

24. The method of any of claims 1-4, wherein the substrate comprises a flexible polymer film having a glass transition temperature of 100 °C or less.

25. The method of any of claims 1-4, wherein the substrate comprises a flexible polymer film having a refractive index of 1.45 or more.

26. The method of claim 5, wherein the voltage applied to the electrode in step (a) and step (b) varies in conjunction with adjustment of the pressure of the process gas.

27. The method of claim 18, wherein the electrode is coupled to a high power pulsed magnetron sputtering (HIPIMS) power supply, and the step of applying a voltage comprises the HIPIMS power supply applying a pulsed DC voltage to the electrode.

28. A thin film deposition method comprising: forming a first film of a metal oxide, a metal nitride, or a combination thereof having a first stress on a substrate, the first film formed by the following steps: (a) placing a substrate proximate to a first electrode coupled to a power supply such that the first electrode and the substrate are separated to leave a gap therebetween; (b) exposing the substrate to a first process gas at a first pressure of 0.8 Torr or less and operating the power supply to apply power to the first electrode having a first voltage of at least 700 volts and a frequency of less than 500 kHz to induce a first plasma in the process gas that occupies the entire gap, wherein the first process gas is selected from the group consisting of an oxygen-containing gas, a nitrogen-containing gas, and mixtures thereof; (c) after step (a), exposing the substrate to a first gaseous metal-containing precursor; (d) alternating steps (b) and (c) a plurality of times; forming a second film of a metal oxide film, a metal nitride film, or a combination thereof having a second stress different in type and amount from the first stress on the first film, the second film formed by the following steps: (e) transporting the substrate to a position proximate to a second electrode such that the second electrode and the substrate are separated to leave a second gap therebetween; (f) exposing the substrate to a second process gas at a second pressure of 0.8 Torr or less different from the first pressure while applying power to the second electrode to induce a plasma state in the second process gas proximate to the substrate, the power applied to the second electrode having a second voltage different from the first voltage and a frequency of less than 500 kHz, wherein the second process gas is selected from the group consisting of an oxygen-containing gas, a nitrogen-containing gas, and mixtures thereof; (g) after step (f), exposing the substrate to the first gaseous metal-containing precursor or a second gaseous metal-containing precursor; and (h) alternating steps (f) and (g) a plurality of times.

29. The method of claim 28, wherein the first electrode is separated from the substrate by 5 cm or less.

30. The method of claim 28 or claim 29, wherein the first film and the second film together form a final thin film, and the first pressure and second pressure are selected to result in the final thin film having a tensile stress of less than 200 MPa, or a compressive stress of less than -200 MPa.

31. The method of claim 30, wherein the final thin film has a density greater than 90% of the theoretical bulk density.

32. The method of claim 30, wherein the final thin film has a thickness of at least 10 nm.

33. The method of claim 28 or 29, wherein the method is performed at a temperature less than 150 °C and the substrate is a temperature sensitive substrate.

34. The method of claim 28 or 29, wherein the first gaseous metal-containing precursor is different from the second gaseous metal-containing precursor.

35. The method of claim 28 or 29, wherein the power source is a continuous DC power source or a pulsed DC power source.

36. The method of claim 28 or 29, wherein the substrate is not cleaned or pretreated.

37. The method of claim 28 or 29, wherein the substrate comprises a flexible polymer film having a glass transition temperature of 100 °C or less.

38. The method of claim 28 or 29, wherein the substrate comprises a flexible polymer film having a refractive index of 1.45 or more.

39. The method of claim 28, wherein the first voltage and the second voltage are both applied at the same constant power or at the same average power over time.

40. The method of claim 28, wherein applying the first voltage to the first electrode comprises applying a constant or pulsed DC voltage between 700 volts and 1500 volts and applying the second voltage to the second electrode comprises applying a constant or pulsed DC voltage between 700 volts and 1500 volts.

41. The method of claim 28, wherein at least one of the first gaseous metal-containing precursor and the second gaseous metal-containing precursor is an amino-based silicon precursor.

42. A barrier film manufactured by the method of claim 1 or 28.

43. The barrier film of claim 42, wherein the barrier film has a stress less than 200 MPa.

44. The barrier film of claim 42, wherein the barrier film has a density greater than 90% of the theoretical bulk density.

45. The barrier film of claim 42, wherein the barrier film has a thickness of at least 1 micron.

46. The barrier film of claim 42, wherein the barrier film has a thickness of at least 10 nm.

47. The barrier film of claim 42, wherein the barrier film is formed directly on the substrate or on an organic smoothing layer that is formed directly on the substrate.

48. The barrier film of claim 42, wherein the barrier film encapsulates the substrate.

49. The barrier film of claim 42, wherein the substrate is rigid.

50. The barrier film of claim 42, wherein the substrate comprises an organic light emitting diode (OLED) display.

51. The barrier film of claim 42, wherein the substrate comprises an illumination panel.

52. The barrier film of claim 42, wherein the substrate comprises an electronic device.

53. The barrier film of claim 42, wherein the substrate comprises a semiconductor device.

54. The barrier film of claim 42, wherein the substrate comprises an optical coating.

55. The barrier film of claim 42, wherein the substrate comprises an optical interference filter.

56. The barrier film of claim 42, wherein the gaseous metal-containing precursor comprises a gaseous silicon-containing precursor, and the plasma comprises an oxygen plasma and the barrier film comprises SiO x .

57. The barrier film of claim 56, wherein the barrier film has a water vapor transmission rate of 3 x 10 -3 g / m 2 per day or less.

58. The barrier film of claim 57, wherein the SiO x The thickness of the barrier film is greater than 300 nm.

59. The barrier film of claim 58, wherein the SiO x The oxygen vapor transmission rate of the barrier film is 5 x 10 -3 cm 3 / m 2 / day or less.

60. The barrier film of claim 57, wherein the barrier film has a thickness of less than 500 Angstroms.

61. The barrier film of claim 56, wherein the barrier film has a refractive index of 1.45 to 1.55 at a wavelength of 633 nm.

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