TW201608691A - Improved through silicon via - Google Patents

Abstract

Through via holes are prepared for metallization using ALD and PEALD processing. Each via is coated with a titanium nitride barrier layer having a thickness ranging from 20 to 200 Å. A ruthenium sealing layer is formed over the titanium nitride barrier layer wherein the sealing layer is formed without oxygen to prevent oxidation of the titanium nitride barrier layer. A ruthenium nucleation layer is formed over the sealing layer wherein the nucleation layer is formed with oxygen in order to oxidize carbon during the application of the Ru nucleation layer. The sealing layer is formed by a PEALD method using plasma excited nitrogen radicals instead of oxygen.

Description

Improved straight through hole 1. Field of invention

The present invention is directed to the preparation of an inner surface of an all-through through-hole for metallization. In particular, one of the inner diameter surfaces and one of the bottom wall surfaces of each of the through holes are coated with a low resistance diffusion barrier layer to prevent dissimilar material from diffusing therethrough. A sealing layer is applied to the diffusion barrier layer to prevent oxidation of the barrier layer. A nucleation layer is applied to the sealing layer. The nucleation layer promotes crystal nucleation of the metal core and reduces pore formation during metallization.

2. Related skills

The through-through vias are used in multilayer or three-dimensional integrated circuits (ICs) to electrically interconnect the isolated circuit layers separated from each other by electrically insulating dielectric layers. The through-through or through-hole through-holes comprise holes through one or more substrate layers that are filled with a low-resistance material such as copper by electroless deposition or electrochemical plating or similar metallization techniques. This hole is metallized. The need to make cheaper, smaller, and lighter electronic products with better performance tends to create smaller through-holes that are distributed over the circuit landscape with smaller hole spacing. This results in the need to provide a through hole having a diameter of 12-30 μm and a through hole depth or length of 200-600 μm. Such through-holes generally refer to a ratio of hole depth to diameter having a diameter greater than about 10 and up to 50. High aspect ratio through holes.

The through vias are formed by wet etching, electrochemical etching, by laser drilling, and more closely by ion beam milling or etching, such as deep reactive ion etching (DRIE). The through hole completely passes through a substrate and exposes the formed inner wall. Since the through hole completely passes through the substrate layer, one of the bottom walls of the through hole is bounded by a conductor portion of one of the circuit layers attached or integrally formed with the dielectric substrate layer. Then, the holes are filled (metallized) by electroplating or the like with a conductive material (for example, copper, tungsten, polyfluorene, gold, etc.), and the conductive material is provided between circuit layers separated by a high-resistance substrate layer. The path of electrical communication.

One of the important performance criteria throughout the through-hole is that the metallized or conductive core material provides a substantially uniform, unconstrained current over the entire diameter and along the entire length of the conductive core. Factors that inhibit current or otherwise degrade the through-hole properties include void formation in the filler material and non-uniform material properties (eg, non-uniform electrical resistance). The formation of pores at the boundary between dissimilar materials is particularly problematic, during which the crystallization of the metal is not uniform. Uneven material properties also occur at the boundaries between dissimilar materials, during which dissimilar materials diffuse across the boundary, mixing dissimilar materials and changing physical properties. This through-hole system is particularly problematic when copper or other metallized material diffuses into the tantalum substrate and degrades performance.

One conventional solution to avoid dissimilar material diffusion across the material boundary is to apply a diffuse barrier layer to the consistent inner diameter surface and to coat the bottom surface thereof to avoid diffusion across the substrate metallization boundary. However, since the through holes are metallized after the substrate and the circuit are connected, the barrier layer applied to one of the bottom surfaces of the through holes needs to have a relatively low resistance because the metal passes through the metal. The current of the core material passes over the barrier layer covering the bottom surface of the through hole. Therefore, a problem of the barrier layer applied to the bottom surface of the through hole is that the current is blocked to the circuit layer unless the barrier layer has a low resistance. Although conventional barrier layers having low electrical resistance can be formed from nitrides such as titanium nitride (TiN) and tantalum nitride (TaN) cobalt nitride (CoN), such barrier layers are conventionally applied by sputtering. However, slopping does not provide good performance for through-holes with high aspect ratios because slopping does not allow the through-holes to be applied to full depth. In particular, more than about 8:1 aspect ratio, splashing is not appropriate. However, even a very high aspect ratio hole provides a complete surface coverage of one of the atomic layer deposition (ALD), which does not allow TiN and other barrier layers to be applied to the inner surface of a high aspect ratio through hole.

While conductive TiN barrier layers are known to avoid diffusion across the substrate metallization boundary and provide acceptable current across the bottom surface, TiN is not ideally suited for metallization adhesion. More particularly, the crystalline nucleation of copper or other conductive metallization material on the TiN barrier layer is unacceptable. In order to improve the metallization adhesion to the TiN barrier layer, it is known to apply a noble metal such as palladium, platinum, cobalt, nickel, and antimony to the barrier layer to provide improved copper adhesion and to reduce corrosion and oxidation of the barrier layer. However, such precious metals are generally not coated by chemical vapor deposition (CVD) or physical vapor deposition (PVD) methods, which provide poor coverage such as splattering through the high aspect ratio through holes.

A method disclosed in U.S. Patent Application Serial No. US 2007/0077750 A1, the disclosure of which is incorporated herein by reference in its entire entire entire entire entire entire entire entire entire entire entire Forming a germanium material on a dielectric material substrate of a cerium oxynitride, a carbon doped cerium oxide or a SiOxCy material substrate, and comprising a germanium, a tantalum nitride, a germanium nitride A Ru layer is formed on the barrier layer material of tantalum, titanium, titanium nitride, tantalum titanium nitride, tungsten or tungsten nitride, and a special example is to deposit the tantalum material by ALD or physical vapor deposition (PVD) method. Pre-formed on the tantalum nitride.

However, Ma et al. disclose dicyclopentanyl compounds such as bis(ethylcyclopentadienyl)fluorene, bis(cyclopentadienyl)fluorene, and bis(pentamethylcyclopentadienyl)fluorene, It is common to deposit a tantalum material that has increased electrical resistance, poor adhesion (not tested by tape), typically requires high adsorption temperatures above 400 °C, and suffers from nucleation delays. Therefore, Ma et al. concluded that a ruthenium containing a pyrrole ligand is more desirable and a deposition temperature below 350 °C is more desirable.

Ma et al. further disclose that by exposing the substrate to a precursor containing a pyrrolyl ligand, the substrate is then exposed to an ammonia plasma, a nitrogen plasma, or a hydrogen plasma in an ALD system. A germanium material is formed on the substrate, the ALD system having a plasma generator external to or incorporated within the ALD system. In particular, Ma et al. seem to recognize that although the tantalum material can be coated with an oxygen precursor, it is disadvantageous that the barrier layer is exposed to oxygen due to the deposition of the barrier layer.

However, even with this recognition, MA et al. uncover a seed layer deposited on the tantalum material by an initial deposition method, and a bulk layer is subsequently deposited thereon by another deposition method. In other words, the second layer taught by MA et al. is applied off-site by methods other than ALD or PEALD.

3. Summary of invention

Based on the problems associated with conventional through-hole surface coating methods and coated through-holes as described above, it is an object of the present invention to apply a conductive diffusion barrier layer throughout the ALD or PEALD deposition process. A through-hole through-hole for metallization is prepared by exposing the surface of the hole.

Another object of the present invention is to apply a conductive nucleation layer to the exposed surface of the through-hole diffusion barrier layer by an ALD or PEALD deposition method to nucleate the conductive core material during metallization.

Another object of the present invention is to protect the barrier layer from oxidation during application of the nucleation layer by applying a sealing layer between the barrier layer and the conductive nucleation layer on the barrier layer, wherein the sealing layer The coating is oxygen free.

The above disadvantages of the prior art can be overcome by the electronic device and coating method disclosed below.

An electronic device includes a through-via through which is formed by an inner diameter surface bounded by an electrically insulating dielectric layer and a bottom wall surface bounded by a conductive portion of a circuit layer. The circuit layer is formed integrally with the dielectric layer. Each through hole is coated with a titanium nitride (TiN) barrier layer having a thickness ranging from 20 to 200 Å. Each of the through vias is coated with a germanium sealing layer formed on the titanium nitride barrier layer, and the sealing layer is formed without oxygen. Each of the through vias is coated with a germanium nucleation layer formed on the germanium sealing layer, and the germanium nucleation layer is formed with oxygen.

The ruthenium seal layer has a thickness ranging from 5 to 10 Å. The ruthenium nucleation layer has a thickness ranging from 50 to 150 Å. The 钌 nucleation layer has a lower resistance than the 钌 sealing layer. Each of the through vias is metallized with copper applied to the germanium nucleation layer.

A method of making a substrate for metallization includes a plurality of through vias applied to a substrate such as an electrically insulating dielectric layer. A layer of material is applied to one of the inner diameter surface and one bottom wall surface of each of the through holes.

A substrate containing such through vias is placed in a processing chamber suitable for deposition of a material by atomic layer deposition (ALD) and by plasma enhanced electron layer deposition (PEALD).

A barrier layer comprising a first material is formed on the inner diameter surface and the bottom wall surface. The first material has a resistance of less than 300 [mu]ohm-cm and is applied at a sufficient thickness to substantially prevent diffusion of a metallized material through the barrier layer.

A sealing layer comprising a second material is applied over the entire barrier layer. The second material has a resistance of less than 300 μ ohm-cm. The deposition of the sealing layer is carried out without substantially causing oxidation of the first material layer.

A nucleation layer comprising a second material is applied over the entire sealing layer. The deposition of the nucleation layer involves oxidation of the carbon.

During deposition of each layer, the processing chamber is at a pressure of less than 1 Torr, and all of the three layers are formed without removing the substrate from the processing chamber. During the formation of all of these layers, the substrate is maintained at a substantially fixed temperature between 200 and 400 °C.

The barrier layer is formed of any one of titanium nitride, titanium, tantalum nitride, tantalum, tungsten nitride, cobalt nitride, and tungsten, and may be formed by ALD or PEALD. The precursor used to form the titanium nitride barrier layer comprises tetrakis(dimethylammonium)titanium (TDMAT) and nitrogen.

The sealing layer is formed from the ruthenium of anaerobic deposition by PEALD. The sealing layer is coated with a first precursor comprising a dicyclopentanyl compound and a second precursor comprising a plasma excited nitrogen group, and no oxygen is used.

Except that the nucleation layer is formed by thermal ALD with oxygen, The nuclear layer is also formed by self-destruction. The nucleation layer is formed using a first precursor comprising a dicyclopentanyl compound and a second precursor comprising un-encapsulated oxygen.

After forming the barrier layer, the sealing layer, and the nucleation layer, the substrate is removed from the processing chamber to metallize the through-holes with the bulk copper.

These and other aspects and advantages will become apparent upon reading the following description in conjunction with the drawings.

100‧‧‧Substrate

105‧‧‧First circuit layer

110‧‧‧Electrically insulating dielectric layer

115‧‧‧through hole through hole

120‧‧‧Electrical Department

125‧‧‧Second semiconductor circuit layer

130‧‧‧Second Conductive Department

135‧‧‧ Conductive core

150‧‧‧Diffusion barrier

155‧‧‧ Sealing layer

160‧‧‧ nucleation layer

200‧‧‧Gas Deposition System

205‧‧‧External chamber wall

210‧‧‧Processing chamber

215‧‧‧Support disk

220‧‧‧Support surface

222‧‧‧Resistive heating element

225‧‧‧ entrance

230‧‧‧ gate valve

235‧‧‧ Non-plasma precursor entry

240‧‧‧Purch precursor entry

245‧‧‧ Plasma generator module

250‧‧‧ top hole

255‧‧‧Processing gas delivery module

260‧‧‧Processing gas supply module

265‧‧‧Export

270‧‧‧vacuum pump

275‧‧‧Export module

280‧‧‧Electronic controller

285‧‧‧Vacuum valve module

290‧‧‧pressure gate

295‧‧‧temperature sensor

4. Brief description of the schema

The features of the present invention are best understood from the detailed description of the present invention and the exemplary embodiments illustrated in the accompanying drawings, wherein FIG. An illustration of a layer of material and an attached circuit layer.

2 depicts an exemplary schematic diagram of a processing chamber and associated module suitable for applying a material deposition layer to a surface of a through-hole by thermal atomic layer deposition (ALD) and plasma enhanced atomic layer deposition (PEALD).

5. Definition

The following definitions are used everywhere, unless otherwise specified by other means:

6. Component number list

Unless otherwise specified, the following component numbers are used throughout:

7. Illustrated straight through hole structure

Referring now to Figure 1, a portion of a multilayer (3-dimensional) integrated circuit (IC) or substrate (100) is shown schematically in side cross-sectional view in accordance with one non-limiting, exemplary embodiment of the present invention. The substrate (100) includes a first circuit layer (105) including a semiconductor material body layer patterned by one or more dielectric material layer electrical interconnect patterns and electrical component patterns, and One or more interconnect patterns are terminated in a conductive layer or in a conductive layer portion (120). The circuit body layer comprises a semiconductor material such as germanium, germanium, gallium arsenide, or the like.

The substrate (100) further includes an electrically insulating dielectric layer (110) comprising an electrically insulating material such as hafnium oxide, tantalum nitride, hafnium oxynitride, and/or carbon doped antimony oxide (such as , SiO _x C _y ), and the like.

A plurality of through hole through holes (115) are formed to completely pass through the dielectric layer (110) at a position corresponding to the conductive portion (120). In addition, the conductive portion (120) The layer is extended by a single layer of conductor material disposed between the insulating dielectric layer (110) and the semiconductor circuit layer (105).

As is known to those skilled in the art, in the end, one of the second semiconductor circuit layers (125) is formed or assembled in a mating contact with the dielectric layer (110) with respect to the first circuit layer (105), and The two circuit layers may include a second conductive portion (130) (or a conductor layer) configured to make electrical contact with each of the through vias (115) relative to the first conductive pad (120).

Therefore, each of the through-hole through-holes (115) includes a through-hole, which is formed to completely extend the direct-on insulating dielectric layer (110) such that the first conductive portion (120) is formed by each through-hole (115) And exposed. The through via thus comprises an inner diameter surface bounded by an electrically insulating material of the dielectric layer (110); a bottom surface bounded by a conductive material of one of the first conductor portions (120).

Through vias are formed by one or more conventional through hole formation techniques, including, by way of example, dip etching, electrochemical etching, by laser drilling, and or by ion beam milling or such as deep reactive ion etching (DRIE). The etching is formed. Each of the through holes is finally filled (metallized) with a conductive material forming one of the conductive core members (135). The illustrated core material comprises copper, tungsten, polyfluorene, gold, but in the embodiment of the invention, copper is preferred. The metal core material can be formed by conventional electroless and electrochemical plating methods. The conductive material core (135) provides a conductive path extending from a first conductive portion (120) to a corresponding opposing second conductive portion (130). In operation, current is supplied to the electrical connection between the first circuit layer (105) and the second circuit layer (125) through the conductive material core (135).

One of the main requirements for the formation of through-holes is to provide a conductive material core (135) that is capable of uniformly and unrestricted current throughout the diameter and overall length of the core material (135). Factors that inhibit current or otherwise degrade the performance of the through-hole are included in the formation of pores in the conductive core (135), and in non-uniform material properties along the length or diameter of the core, for example, non-uniform electrical resistance. One of the main factors of pore formation during metallization is the adhesion of the conductive core material to the inner diameter surface and the bottom wall surface of the through hole. This problem is solved by the present invention by providing a nucleation or seed layer (160) [solid black] which is bonded to the core material (135) at the inner diameter surface and the bottom wall surface of the through hole (115). contact. The nucleation layer (160) is assembled to crystallize the metal conductor that is used to metallize the core material. The presence of the nucleation layer (160) improves the adhesion of the material of the metal core material (135) to the inner diameter of the through hole and the surface of the bottom wall, and this reduces the formation of voids at the edge of the boundary of the core material (135). In particular, the present invention forms a nucleation layer by an atomic layer deposition method in situ.

One of the major factors in the production of non-uniform material properties in or near the core material (135) is the diffusion of the conductive core material into the electrically insulating dielectric material of the dielectric layer (110) during metallization. This problem is solved by the present invention by providing a diffusion barrier layer (150) [solid gray] in the through hole in the inner diameter surface and the bottom wall surface of the through hole, wherein the diffusion barrier layer (150) is deposited by ALD or PEALD. The diffusion layer (150) is formed with a sufficient material thickness to substantially prevent the dissimilar material (especially copper) from corroding the diffusion layer (150). The diffusion layer (150) is formed from a material having a resistance of less than about 300 ohm-cm so as to impede current flow over the diffusion layer at the electrical interface between the conductive core (135) and the first conductive portion (120) ( 150) The bottom surface is minimal. Preferably, the diffusion layer (150) It is formed by coating a material by a thermal ALD method or a PEALD method from a reaction temperature range of less than 500 ° C and preferably from 250 to 350 °.

According to one non-limiting exemplary aspect of the invention, the through-hole through-holes (115) are formed as follows. Each through via is formed by a suitable hole formation technique as described above. Although the different through-hole through-holes (115) may have the same or different hole diameters, the diameter of any particular through-holes preferably ranges between 12 and 30 [mu]m, but larger diameter through-holes may be processed by the present invention. The depth or length of each of the through holes (115) is substantially equal to the thickness of the dielectric layer (110). In the non-limiting exemplary embodiment of the present invention, the through holes of the high aspect ratio are between 200 and 600 μm. The through-holes, but shorter lengths, can be processed by the present invention. The center-to-center pitch size between the through holes (115) is 50 μm or more, but a smaller center pitch size through hole can be processed by the present invention. Therefore, if a through-hole having a higher aspect ratio can be formed, the present invention is suitable for a through-hole having a very high aspect ratio ranging from a hole diameter of up to 50 or more to a hole diameter to a hole depth.

Each of the through holes (115) includes a diffusion barrier layer (150) directly coated on the inner surface of the through hole, and is included on the inner diameter surface formed by the dielectric layer (110) and by the conductive portion (120) ) formed on the bottom surface of the through hole. The barrier layer (150) is formed to avoid or substantially reduce diffusion of the metallized material (preferably copper) through the barrier layer (150) during core metallization. The barrier layer (150) includes a material having a sufficiently low electrical resistance to provide substantially unimpeded current through the bottom surface of the diffusion layer. In a non-limiting, exemplary embodiment, the barrier layer (150) comprises titanium nitride (TiN) applied to a range of 20 to 200 Å (2 to 20 nm). The thickness of the layer. The TiN barrier layer (150) is preferably applied by any one of a thermal atomic layer deposition (ALD) method or a plasma enhanced atomic layer deposition (PEALD) method. In addition, the barrier layer (150) comprises TiN coated to a layer thickness in the range of 20 to 200 Å (2 to 20 nm) by a plasma enhanced atomic layer deposition (PEALD) method. Other exemplary barrier layer materials suitable for the present invention include titanium, tantalum nitride, tantalum, tungsten nitride, and tungsten formed by ALD or PEALD methods. In each case, the barrier layer has a resistance of less than 300 ohm-cm and preferably.

Each of the through holes (115) includes a sealing layer (155) [white area] which is directly applied to the diffusion barrier layer (150) between the barrier layer (150) and a nucleation layer (160) as follows. . The sealing layer (155) is applied on the inner diameter surface and the bottom wall surface of the barrier layer (150) in the through hole (115), and comprises a material having a sufficiently low electrical resistance, for example, having less than 300 ohm-cm. The resistor is such that the bottom wall surface allows a substantially unimpeded current to pass. The sealing layer (155) is formed without oxygen and is specially coated on the barrier layer to coat the nucleation layer (160) to prevent oxidation of the barrier layer material. The coating of the nucleation layer (160) is as follows. It is deposited with oxygen. Oxidation of the barrier layer tends to increase the electrical resistance of the barrier layer, which thereby impedes current flow through the barrier layer (150) across the bottom surface.

The sealing layer (155) comprises ruthenium (Ru) which is applied at a sufficient layer thickness to avoid oxygen from reacting with the surface of the barrier layer during coating of the nucleation layer (160). In a non-limiting exemplary embodiment of the invention, a sealing layer (155) comprising Ru is applied at a layer thickness ranging from 5 to 10 Å (0.5 to 1.0 nm), wherein the coating of the sealing layer is not blocked. The layer material is exposed to oxygen. The sealing layer (155) is formed by a PEALD method using a dicyclopentanyl compound such as bis(ethylcyclopentadienyl)fluorene, bis(cyclopentadienyl)fluorene, and bis(pentamethyl). The first ruthenium of one or more of cyclopentadienyl) is formed. Thereafter, a second precursor comprising a plasma-excited nitrogen group is introduced into the processing chamber to complete a single monolayer of Ru, and the second precursor is self-plasma-excited N ₂ gas, ammonia ( NH ₃ ), and hydrazine, or any combination of these are produced.

Each of the through holes (115) includes a nucleation layer (160) which is directly applied to the inner diameter surface of the barrier layer (150) in the through hole (115) and the sealing layer (155) on the surface of the bottom wall. The nucleation layer (160) comprises a material having sufficient bottom resistance to provide a substantially unimpeded current flow through the bottom surface of the nucleation layer, for example, less than 300 ohm-cm. A nucleation layer (160) is interposed between the conductive core material (135) and the sealing layer (155) and is specifically provided to cause crystallization of the material of the conductive core material to nucleate during metallization. In a non-limiting exemplary embodiment of the invention, the material of the nucleation layer is Ru, which is applied by a thermal ALD process, including oxidation of carbon. The nucleation layer is applied to a thickness in the range of 50 to 150 Å (5-15 nm). Although both the sealing layer (155) and the nucleation layer (160) are Ru layers, the thickness of the nucleation layer is less than the resistance of the sealing layer due to different deposition methods. The lower resistance portion of the nucleation layer (160) occurs because the ruthenium proton ligand is more reactive toward oxygen than to nitrogen. Therefore, the nucleation layer (160) formed with oxygen forms a reduced impurity and a corresponding reduced resistance as compared with the sealing layer (155) formed with nitrogen. Impurities in the nucleation layer reduce copper nucleation during further metallization.

Although Ru is a preferred material for forming a seed layer and a nucleation layer, other material candidates may be used without departing from the invention from various chemistries, and such unrestricted inclusion of palladium (Pd), platinum (Pt), rhodium (Rh), iridium (Ir), silver (Ag), cobalt (Co), molybdenum (Mo), chromium (Cr), and tungsten (W). Each through hole (115) contains A conductive metal core (135). In a non-limiting exemplary embodiment of the present invention, the metal core material (135) comprises bulk copper, and the bulk copper core material (135) is a conventional electroless deposition method using a redox reaction, a physical deposition method, an electron beam evaporation method, Electrochemical plating (ECP) method, chemical vapor deposition (CVD) method, etc. are formed; In addition, other conductive core materials such as tungsten, polyfluorene, and gold may be used without departing from the invention.

More particularly, each of the barrier layer (150), the sealing layer (155), and the nucleation layer (160) is in the same ALD processing chamber without removing the substrate (100) from the ALD method chamber. form. Furthermore, the ALD processing chamber contains a plasma product and is configured to perform a material deposition cycle by thermal ALD and or by PEALD. After the application of the barrier layer, the sealing layer, and the nucleation layer is completed, the substrate (100) is removed from the ALD processing chamber to another location, and the core material is metallized with copper. Other core metallization materials can also be used.

According to another aspect of the invention, the barrier layer (150), the sealing layer (155) and the nucleation layer (160) are coated by different atomic layer deposition (ALD) and plasma enhanced atomic layer deposition (PEALD) methods. . More specifically, the titanium nitride barrier layer (150) is formed simultaneously on all of the through-hole through-holes by the first ALD coating sequence, and the germanium sealing layer (155) is implemented by not exposing the barrier layer to oxygen. The second PEALD coating sequence is formed simultaneously on the barrier layer (150) of all of the through vias, and the nucleation layer (160) is simultaneously all of the through pass including the third ALD coating sequence for carbon oxidation. The hole is formed through the sealing layer (150) of the through hole.

8. Exemplary gas deposition system and mode of operation

In accordance with the present invention, a substrate (100) comprising an electrically insulating dielectric layer (110) and an attached circuit layer (105) is fabricated by known conventional circuit fabrication techniques. In a non-limiting, exemplary embodiment, the dielectric layer (110) comprises an electrically insulating dielectric material such as hafnium oxide, hafnium nitride, hafnium oxynitride, and/or carbon doped antimony oxide (such as , SiO _x C _y ), and the like. The substrate (100) may comprise a disk wafer having a diameter of one of 25, 50, 100, 200, or 300 mm. However, without departing from the invention, the dielectric layer (110) can have other shapes and be formed from other materials.

Referring now to Figure 2, a side cross-sectional view of a non-limiting exemplary gas deposition system (200) is shown schematically. The system (200) includes an outer chamber wall (205) that surrounds a processing chamber (210). A support disk (215) disposed within the processing chamber (210) provides a support surface (220) that supports a substrate (100) thereon during a gas deposition coating cycle. The support disk (215) may further comprise a resistive heating element (222) disposed under the support surface (220) operable to heat the substrate (100) supported on the support surface (220) to a particular gas deposit The coating material and the gas deposition method to be carried out will require the desired reaction temperature.

The system (200) includes a loading port (225) having a gate valve (230) operable to pass a substrate (100) to be coated by gas deposition through the outer chamber wall (205) to Or a plurality of substrates (100) to be deposited and deposited are placed on the support surface (220). The loading and unloading of each substrate can be performed manually, for example, using wafer pliers or the like to pass the substrate to be deposited and coated through the port gate valve (230) and the loading port (225). In addition, an automated wafer loading and raking device (not shown) can be used in combination with the deposition system (200) and can be automatically loaded with substrates at the beginning of a gas deposition coating cycle, as well as for gas deposition. The substrate is automatically removed at the end of the coating cycle. In particular, an automated loading and unloading system advantageously enables the substrate to be loaded and raked under unbroken vacuum, thereby reducing pumping time between deposition cycles.

The system (200) includes a non-plasma precursor inlet (235) that passes directly through the outer wall (205) for direct delivery of the first and second precursors to the processing chamber (210) without plasma excitation. . The system (200) includes a plasma precursor inlet (240) that passes a first or second precursor to the plasma generator module through an outer wall of a plasma generator module (245) (245) ) is excited by the power supply slurry. The precursor delivered to the plasma generator module (245) enters the processing chamber (210) via a top hole (250).

Each precursor inlet is in fluid communication with a process gas delivery module (255) and incorporates a process gas supply module (260). The process gas supply module (260) houses a container filled with various processing materials, which may include a container filled with a processing material in a liquid, solid, and gaseous state. The process gas delivery module (255) includes one or more bubblers or the like (not shown) for producing various precursor supplies, for example, extraction from solid or liquid precursor sources; and various flow control elements, including a pulse valve (not shown) for delivering a pulse of precursor vapor to the appropriate precursors (235) and (240), wherein each precursor pulse has a desired pulse, which provides a suitable The precursor vapor of the content of the particular ALD or PEALD coating process being practiced.

Additionally, the process gas supply module (260) includes or is coupled to an inert gas supply, and the gas delivery module (255) is configured to deliver inert gas to each of the precursors (235) and (240) By. The inert gas flow is regulated by a gas delivery module (255) that is operable to control the inert gas continuously Flow is delivered through each of the precursors, or the inert gas stream is adjusted to allow the batch of inert gas to pass through any one or both of the precursor inlets (235) and (240) to the desired inertness in the processing chamber (210). Gas pressure and flow rate. In either case, the inert gas stream can be used as a carrier gas for carrying the precursor vapor to the processing chamber (210). Additionally, between the precursor cycles, only inert gas flows through the processing chamber to flush or flush the processing chamber (210).

The PEALD system (200) includes an outlet (265) that is in fluid communication with a vacuum pump (270) and the vacuum pump (270) operates to cause the processing chamber by removing gas from the processing chamber via the outlet (265) ( 210) Take time out. The gas removed from the processing chamber contains any unreacted precursor material and any reaction by-products during the deposition cycle. In addition, an outlet module (275) includes a pressure brake (290) or the like that provides local gas pressure readings to an electronic controller (280) and a vacuum valve module operable by the electronic controller (280) (285) to seal a conduit leading to the vacuum pump. Additionally, one or more temperature sensors (295) are provided to monitor the local temperature and report temperature information to the electronic controller (280).

In operation, the system (200) can be used to apply a coating of film material to the substrate (100) as described above. The substrate (100) is supported on the support disk (215), and the first circuit layer (105) is in contact with the support surface (220), and the dielectric layer (110) faces the top hole (250) upward. The process gas entering the chamber (210) through the precursor (235) and the top hole (250) expands the filling chamber (210) and impacts a top surface of the dielectric layer (110), and some processing gas enters the through hole ( 115) Reacts with its surface. The processing gas reacts with any exposed surface of the substrate (100) and includes at least a top surface of the substrate layer (110) and an inner wall surface of the through hole (115) A thin film deposition layer is formed on all of the exposed surfaces (including the bottom surface formed by the first conductive portion (120)).

As is known, each ALD coating cycle is based on two self-limiting reactions. a first self-limiting reaction between a first precursor and an exposed surface of a substrate produces a first semi-monolayer of solid material on the exposed surface of the substrate, and a second precursor and the exposed surface of the substrate A second self-limiting reaction produces a second semi-monolayer of solid material on the exposed surface of the substrate. More specifically, a separate and independent self-limiting precursor reaction with the exposed surface is performed to deposit a single monolayer of the desired material onto the exposed surface. Furthermore, due to the self-limiting nature of the reaction, the thickness of a single layer of a single material is substantially predetermined and approximately equal to a single atomic layer of the material, i.e., each single layer has an approximate thickness of from 0.5 to 1.5 Å, which is at least It includes temperature, precursor vapor pressure and volume, gas pressure inside the processing chamber, and various growth conditions for exposure time. Because for most stresses, at least 5 single layer coatings are required to provide a minimum functional material coating thickness, and the two self-limiting reactions are repeated 5 times to allow 5 coating layers to be deposited to be single layered. Deposition. More generally, however, an ALD coating thickness of from 100 to 200 monolayers and in some cases up to about 1000 monolayers is used to coat the substrate with a desired surface coating for use with a surface coating. Material properties.

The system (200) is configured for automatic coating cycle operation based on an operating mode menu stored in the electronic controller (280) and selectable or programmable by the user. In a non-limiting example, a user may enter or select a processing pattern (eg, ALD, PEALD) and select a chemical action, such as a first precursor, a second precursor, a reaction temperature, and a desired list The number of layers. Additionally, the inert gas flow and module parameters can be selected by the user for exposure time, and for long exposure times, the vacuum outlet valve (285) can be closed during the deposition cycle. Once the coating cycle parameters are selected, the system (200) performs the selected coating sequence by automatically applying a single layer to the desired surface coating to fully form to the desired number of monolayers. Thereafter, the user can remove the substrate, install another substrate, and repeat the same coating cycle for a new substrate, or other coating cycles can be implemented to add additional deposition coatings to the same substrate.

In addition, the user can input a series of coating cycles, wherein the first material is applied to the exposed surface to a desired thickness or number of single layer cycles, and thereafter, the second material is applied to the exposed surface, On a layer of material, to a desired thickness or number of single layer cycles, and so on, to coat a further coating of material. For the exemplified coating, the user inputs two or more coating programs, and each program specifies a different processing pattern (if any), a different chemistry for the one or more coating materials. Or a combination of the first and second precursors (if any), a different reaction temperature (if any), and a different desired thickness or number of monolayers, if any. Once the coating cycle parameters for two or more coating cycles are selected and input, the system (200) automatically implements the first coating sequence until the first surface coating is fully formed to the desired number of monolayers. Thereafter, the system (200) automatically implements the second coating sequence using different parameters until the second surface coating is fully formed to the desired number of monolayers. Thereafter, the system (200) automatically implements the third coating sequence using different parameters until the third surface coating is fully formed to the desired number of monolayers.

Thereafter, the user can remove the substrate, install additional substrates, and It repeats two or more coating cycles for a new substrate.

An exemplary gas deposition system (200) that can be used to apply three or more material coating layers to the inner surface of a through-hole according to the present invention is described in the related published U.S. Patent Application Serial No. 2010/018, 325, the name of which is incorporated herein by reference. A plasma atomic layer deposition system and method, filed on December 28, 2009 by Becker et al., the entire disclosure of which is hereby incorporated by reference.

9. An exemplary coating method for forming a barrier layer

In one non-limiting exemplary embodiment of the invention, the inner surface of the through-hole is coated with a barrier layer (150) comprising titanium nitride (TiN). The barrier layer (150) is applied to the thickness of the layer ranging from 20 to 200 Å using the system (200) described below.

- the substrate (100) is embedded in the processing chamber (210) via the gate valve (230) and the inlet (225), and placed on the support surface (220), and the top surface of one of the dielectric layers (110) faces the top hole (250), that is, the open end of the through hole faces the top hole (250). In this example, the substrate layer (100) is a 100, 200 or 300 mm wafer, and each wafer is processed one at a time. However, a plurality of substrates (100) can be processed in batches without departing from the invention.

- The gate valve (230) is automatically or closed by the user. The system (200) operates to heat the substrate (100) to a desired reaction temperature, and the vacuum pump (270) operates continuously to evacuate the chamber to a desired reaction pressure. In this example, the preferred reaction or substrate temperature for TiN barrier layer deposition is between 270 ° C and 400 ° C, and the desired reaction pressure is between 1 and 100 μtorr (1.33-133.32 mPa). However, other reaction temperatures TiN (for example, ranging from 200 to 500 ° C) and other reaction pressures (for example, ranges) for TiN are not deviated from the present invention. It can be used from 1 to 10,000 μtorr).

- the chamber is flushed by a continuous or intermittent flow of inert gas delivered to the chamber via one or both of the precursor inlets (235) and (240) or via another orifice (not shown) In addition to moisture and other pollutants.

A first thermal ALD coating cycle is initiated to apply a TiN barrier layer to the exposed surface of the substrate (100).

- a first metal organic precursor comprising tetrakis(dimethylammonium)titanium (TDMAT) is introduced into the processing chamber via a first precursor inlet (235). The first precursor is introduced by generating a vapor pulse by operating a pulse valve (not shown) for a pulse time, wherein the pulse time is proportional to the volume of the first precursor vapor contained in the vapor pulse. . The first precursor pulse can be mixed with a continuous stream of inert gas flowing from the process gas delivery module (255) to the first precursor inlet (235).

- (1) The first precursor reacts with the exposed surface of the substrate (100) for a period of time equal to the predetermined exposure time. Exposure time can be a function of system design. For example, the exposure time of the precursor pulse to the substrate can be substantially equal to the total volume of the straight air pump (270) being equal to the total volume of the processing chamber (210) plus the gas conduit that is directed to the processing chamber via the outlet (265). The time it takes for the volume of gas to be volume. In this case, the exposure time can be on the order of 10-2000 msec. For longer exposure times, for example, up to about 60 seconds, the vacuum valve (285) can be closed to prevent the precursor from leaving the processing chamber for a desired exposure time.

Preferably, each precursor pulse time (pulse valve opening time) is optimized to provide a sufficient precursor vapor volume in a single pulse to substantially saturate or expose the exposed surface of the substrate to be coated Complete reaction. In other words, Each precursor pulse contains sufficient precursor to complete the self-limiting reaction with the exposed surface during the time taken by the precursor pulse through the processing chamber (210).

- (2) A first flush cycle is performed in which the processing chamber (210) is flushed to remove all traces of the first precursor. This may include simply flushing the vacuum pump and continuous inert gas flow to remove a gas volume equal to 2-5 times the volume of the processing chamber (210) and the flow conduit leading to the chamber.

- (3) The second precursor comprising nitrogen is introduced into the processing chamber via the first precursor inlet (235). The second precursor system such as ammonia (NH ₃₎ by the pair of the pulsing valve (not shown) is operated for a time pulse is generated one pulse is introduced vapor, wherein the vapor system and the pulse time of the second pulse contained in the first The volume of the mass vapor is proportional. The second precursor pulse can be mixed with a continuous inert gas stream flowing from the process gas delivery module to the first precursor inlet (235).

- the second precursor can react with the exposed surface of the substrate (100) for a period of time equal to the predetermined exposure time.

- (4) A second flush cycle is performed in which the processing chamber (210) is flushed to remove all traces of the second precursor.

The above 4-step cycle is an example of a thermal ALD deposition process that can be used to create a single monolayer of barrier layers (150), wherein the barrier layer comprises TiN. This 4-step process is repeated to apply another monolayer until a desired barrier layer thickness is achieved.

In another embodiment of the coated barrier layer (150) of the present invention, TiN can be applied by PEALD. While the same 4-step process is implemented, the second precursor is replaced with a plasma-excited nitrogen group that is delivered from the plasma generator (245) to the processing chamber (210) via the top hole (250). The plasma group is derived from a second precursor that is delivered from the process gas delivery module (255) to the plasma generator (245) via the second precursor inlet (240). In particular, the second precursor may comprise nitrogen (N ₂ ), a mixture of nitrogen and hydrogen, or ammonia. In all other respects, the above described methods for forming the barrier layer are substantially identical.

In any of the above examples, the precursor is preheated to about 75 ° C to achieve a desired vapor pressure for the pulse. The minimum barrier layer thickness (about 20 Å) is achieved by performing about 34-40 single layer coatings, wherein each single layer has a thickness of about 0.5 to 0.6 Å. The maximum barrier layer thickness (about 200 Å) is achieved by performing about 333-400 single layer coatings.

10. An exemplary coating method for forming a sealing layer (oxygen free)

In one non-limiting, exemplary embodiment of the invention, the inner surface of the through-hole is coated with a seal layer (155) comprising ruthenium (Ru). The sealing layer (155) is applied to the thickness of the layer ranging from 5 to 10 Å using the above system (200) as described below. The substrate temperature can be changed to a temperature ranging from 250 to 350 ° C to apply a sealing layer (155). However, in a preferred method, the same deposition temperature of about 300 ° C is used to deposit the barrier layer, the sealing layer, and the nucleation layer.

- (1) The first precursor comprising the dicyclopentanyl compound is introduced into the processing chamber via the first precursor inlet (235). The dicyclopentanyl compound does not include, without limitation, bis(ethylcyclopentadienyl)fluorene, bis(cyclopentadienyl)fluorene, and bis(pentamethylcyclopentadienyl)fluorene. In particular, the chemical compound of bis(ethylcyclopentadienyl)fluorene = (EtCp)2Ru=Ru(C5H4C2H5)2, bis(cyclopentadienyl)fluorene=Cp2Ru=Ru(C5H5)2, and double ( Pentamethylcyclopentadienyl) 钌=(Me5Cp)2Ru=Ru(C5(CH3)5)2

- a first precursor to operate a pulse by operating a pulse valve (not shown) A vapor pulse is introduced in time, wherein the pulse time is proportional to the volume of the first precursor vapor contained within the vapor pulse. The first precursor pulse can be mixed with a continuous inert gas stream flowing from the process gas delivery module to the first precursor inlet (235). The dicyclopentanyl compound pulse reacts with the surface of the barrier layer (150) to form a first semi-monolayer of the sealing layer (155).

- (2) A first flush cycle is implemented in which the processing chamber (210) is flushed to remove all traces of the first precursor.

- (3) A second precursor comprising a mixture of nitrogen and hydrogen gas flows into the plasma generator (245) via the second precursor inlet (240). The plasma generator is ignited to excite nitrogen and hydrogen, which react with the exposed surface of the substrate to complete the formation of the first monolayer of Ru. Hydrogen is introduced into the first Ru semi-monolayer deposited on the TiN barrier layer by the first precursor, but the coating step can be carried out without hydrogen without departing from the invention. The finished single layer has a thickness of about 0.5 Å and is formed without oxygen to avoid oxidation of the barrier layer (150). The second precursor may comprise any of N ₂ gas, ammonia, and hydrazine, which are excited by a plasma source.

- (4) A second flush cycle is performed in which the processing chamber (210) is flushed to remove all traces of the second precursor.

The 4-step cycle described above is an example of a single single layer PEALD deposition process that can be used to create a sealing layer (155) wherein the sealing layer comprises Ru which is formed by a dicyclopentanyl compound without oxygen. This 4-step process is repeated with additional Ru monolayers until a desired seal layer thickness is achieved. The minimum seal layer thickness (about 5 Å) is achieved by performing 10 single layer coatings, wherein each single layer has a thickness of about 0.5 Å. The maximum seal layer thickness (about 10 Å) is achieved by performing about 20 single layer coatings. a thicker seal coating It can be used without departing from the invention.

11. An exemplary coating method for forming a nucleation layer (with oxygen)

In one non-limiting exemplary embodiment of the invention, the inner surface of the through-hole that has been coated with the barrier layer (150) and the sealing layer (155) is coated with a ruthenium-containing layer (160). The nucleation layer (160) is applied to the Ru sealing layer (155) in a thickness ranging from 50 to 150 Å using the system (200) described above. The substrate temperature can be varied to a temperature in the range of 250 to 350 ° C to coat the nucleation layer (160). However, a preferred method is to deposit a barrier layer, a sealing layer, and a nucleation layer on a substrate maintained at the same temperature (e.g., 300 ° C).

- (1) The first precursor comprising the dicyclopentanyl compound is introduced into the processing chamber via the first precursor inlet (235). The first precursor is introduced by generating a vapor pulse by operating a pulse valve (not shown) for a pulse time, wherein the pulse time is proportional to the volume of the first precursor vapor contained in the vapor pulse. . The first precursor pulse can be mixed with a continuous inert gas stream flowing from the process gas delivery module to the first precursor inlet (235). The dicyclopentanyl compound pulse reacts with the surface of the sealing layer (155) to form the first semi-monolayer of Ru of the nucleation layer (160).

- (2) A first flush cycle is implemented in which the processing chamber (210) is flushed to remove all traces of the first precursor.

- (3) A second precursor comprising oxygen is introduced into the processing chamber via a first precursor inlet (235). The second precursor is introduced by generating a vapor pulse by operating a pulse valve (not shown) for a pulse time, wherein the pulse time is proportional to the volume of the second precursor vapor contained in the vapor pulse. . The second precursor pulse can flow from the process gas delivery module to the first precursor inlet (235) A continuous stream of inert gas is mixed. Oxygen reacts with the surface of the first monolayer formed by the first precursor to complete the formation of the first semi-monolayer of Ru formed with oxygen. The oxygen precursor can be used without oxidizing the TiN barrier layer because the sealing layer (155) prevents oxygen from reacting with the barrier layer (150). Further, during metallization of the conductive metal core (135), oxygen oxidizes the carbon during formation of a nucleation layer that supports copper crystal nucleation and adhesion to the nucleation layer (160). The characteristics of this reaction are as follows:

. O2 pulse: O2->O (adsorption)

. Ru precursor pulse: Ru(C5H4C2H5)2(adsorption)+O(adsorption)->Ru+CO2+H2O

- (4) A second flush cycle is performed in which the processing chamber (210) is flushed to remove all traces of the second precursor.

The 4-step cycle described above is an example of a thermal ALD deposition process that can be used to produce a single monolayer of Ru nucleation layer (160), wherein the nucleation layer comprises Ru, which is formed with oxygen. This 4-step process is repeated to apply additional monolayers until a desired nucleation layer thickness is achieved. The minimum nucleation layer thickness (about 50 Å) is achieved by performing about 100 single layer coatings, wherein each single layer has a thickness of about 0.5 Å. The maximum nucleation layer thickness (about 150 Å) is achieved by performing about 300 single layer coatings. The thicker nucleation layer coating can be used without departing from the invention.

More generally, metal-containing dicyclopentanyl compounds such as bis(ethylcyclopentadienyl)fluorene, bis(cyclopentadienyl)fluorene, and bis(pentamethylcyclopentadienyl)fluorene The formation of the sealing layer and the nucleation layer is preferred. However, other ruthenium precursors can be used which comprise pyrrole ruthenium precursors containing ruthenium and at least one pyrrolyl ligand. Methylcyclopentadienylpyrrolyl hydrazone ((MeCp)(Py)Ru) derived.

It is also apparent to those skilled in the art that although the invention has been described above in terms of preferred embodiments, it is not limited thereto. The various features and aspects of the invention described above may be used individually or in combination. Furthermore, although the present invention is described in the context of its implementation in a particular environment and for special applications (eg, application of a deposition coating to the inner surface of a through-hole through-hole), it is familiar to the art. It will be appreciated that its usability is not limited in this respect, and that the present invention can be advantageously utilized in any number of environments and implementations that are intended to form a deposited layer in a manner that improves IC performance. Therefore, the scope of the invention as set forth below is to be construed as the full scope and spirit of the invention disclosed herein.

100‧‧‧Substrate

105‧‧‧First circuit layer

110‧‧‧Electrically insulating dielectric layer

115‧‧‧through hole through hole

120‧‧‧Electrical Department

125‧‧‧Second semiconductor circuit layer

130‧‧‧Second Conductive Department

135‧‧‧ Conductive core

150‧‧‧Diffusion barrier

155‧‧‧ Sealing layer

160‧‧‧ nucleation layer

Claims (29)

An electronic device comprising a through-through hole formed by an inner diameter surface and a bottom wall surface, wherein all surfaces are coated as follows: a titanium nitride barrier layer having a thickness ranging from 20 to 200 Å; a sealing layer formed on the titanium nitride barrier layer, wherein the sealing layer is formed without exposing the barrier layer to oxygen; and a germanium nucleation layer is formed on the sealing layer Above, wherein the nucleation layer is formed by oxygen. The electronic device of claim 1, wherein the ruthenium sealing layer has a thickness ranging from 5 to 10 Å. The electronic device of claim 2, wherein the enamel layer has a thickness ranging from 50 to 150 Å. The electronic device of claim 3, wherein the 钌 nucleation layer has a resistance less than the resistance of the 钌 nucleation layer. The electronic device of claim 4, wherein the through-via is metallized with copper by applying the copper to the tantalum nucleation layer. An integrated electrical device assembly comprising: - a dielectric substrate layer comprising an electrically insulating material; - a circuit layer supported on the dielectric substrate layer, comprising an electrical device and an interconnect pattern a patterned semiconductor material layer; - a conductive layer disposed between the dielectric layer and the circuit layer, comprising at least a conductive layer portion in electrical communication with at least one of the interconnect patterns; a through-hole through-hole that completely passes through the dielectric substrate layer to the conductive layer, including an inner diameter surface bounded by the dielectric substrate layer, and one of the conductive layer portions a bottom surface; a barrier layer formed on each of the inner diameter surface and the bottom wall surface, comprising a first material having an electrical resistance of less than 300 μ ohm-cm, wherein the barrier layer is sufficient a layer thickness is formed to prevent diffusion of the through-hole metallization material therethrough; - a sealing layer formed on the inner diameter surface and the barrier layer layer on each of the bottom wall surfaces, comprising one having less than 300 μohm- a second material of the resistance of cm, wherein the formation of the sealing layer is performed without exposing the first material layer to oxygen; a nucleation layer formed on the inner diameter surface and the bottom wall surface The second sealing layer comprises a second material, wherein the nucleating layer is formed to oxidize carbon. The semiconductor substrate of claim 6, wherein the first material comprises any one of titanium nitride, titanium, tantalum nitride, tantalum, tungsten nitride, cobalt nitride, and tungsten. The semiconductor substrate of claim 7, wherein the barrier layer has a thickness between 19 and 201 Å. The semiconductor substrate of claim 7, wherein the second material comprises ruthenium. The semiconductor substrate of claim 9, wherein the sealing layer has a thickness between 4 and 11 Å, and the nucleation layer has a thickness between 49 Å and 151 Å. The semiconductor substrate of claim 9, wherein the sealing layer is deposited on the exposed surface of the barrier layer to form a plurality of monolayers, wherein each of the plurality of monolayers is Dicyclopentane The compound reacts with the exposed surfaces of the through holes, and thereafter, the nitrogen groups generated by the plasma are formed by reacting with the exposed surfaces of the through holes. The semiconductor substrate of claim 6, wherein the through hole through hole has a diameter of less than 30 μm and a through hole depth of more than 200 μm. The semiconductor substrate of claim 6 wherein the metallization material comprises bulk copper. A method for preparing a through-hole through-hole for metallization, wherein the through-hole comprises an inner diameter surface and a bottom wall surface, the method comprising: - placing a substrate comprising at least a through-hole through-hole In a processing chamber, the processing chamber is adapted to coat a material deposition layer by atomic layer deposition (ALD) and by plasma enhanced atomic layer deposition (PEALD); - at least the through hole through hole Forming a barrier layer comprising a first material on each of the inner diameter surface and the bottom wall surface, wherein the first material has a resistance of less than 300 μohm-cm and is coated with a sufficient thickness to avoid The metallized material is diffused through the barrier layer; a sealing layer comprising a second material is formed on the entire barrier layer, wherein the second material has a resistance of less than 300 μohm-cm, and the deposition of the sealing layer is The first material layer is not exposed to oxygen; and a nucleation layer comprising the second material is formed over the entire sealing layer, wherein the formation of the nucleation layer comprises oxidizing carbon. The method of claim 14, further comprising: - forming a period of each of the barrier layer, the sealing layer, and the nucleation layer Maintaining the processing chamber at a pressure of less than 1 Torr; and - forming the barrier layer, the sealing layer, and each of the nucleation layers without removing the substrate from the processing chamber By. The method of claim 15, further comprising maintaining the substrate at a fixed temperature during formation of the barrier layer, the sealing layer, and the nucleation layer. The method of claim 16, wherein the fixed temperature is between 199 and 401 °C. The method of claim 17, further comprising maintaining the substrate at at least two different fixed temperatures during formation of at least two of the barrier layer, the sealing layer, and the nucleation layer. The method of claim 18, wherein each of the at least two different fixed temperatures is at a temperature between 199 and 501 °C. The method of claim 14, further comprising forming the barrier layer from at least one of titanium nitride, titanium, tantalum nitride, tantalum, tungsten nitride, cobalt nitride, and tungsten. The method of claim 20, further comprising forming the barrier layer by thermal atomic layer deposition. The method of claim 20, further comprising forming the barrier layer by plasma enhanced atomic layer deposition. The method of claim 14, wherein the first material comprises titanium nitride, the method further comprising the step of forming the barrier layer by: - making the inner diameter of the at least all through hole through each of the holes The surface and the surface of the bottom wall are exposed to a first precursor comprising tetrakis(dimethylammonium)titanium (TDMAT) for a duration sufficient to complete the TDMAT and the inner diameter surface And an exposure time of the self-limiting reaction of the bottom wall surface; - flushing the TDMAT and reaction by-products from the processing chamber; - the inner diameter surface and the bottom wall of each of the at least all through holes The surface is exposed to a second precursor comprising nitrogen for a period of exposure to complete the self-limiting reaction of the nitrogen with the inner diameter surface and the bottom wall surface; - flushing the nitrogen and reaction by-products from the processing chamber ;- Repeat the above exposure and rinsing steps until the thickness of the first material is between 19 and 201 Å (1.9-20.1 nm). The method of claim 23, further comprising forming the barrier layer by a thermal atomic layer deposition method, wherein the second precursor comprises ammonia (NH ₃ ). The method of claim 23, further comprising forming the barrier layer by a plasma enhanced atomic layer deposition method, wherein the second precursor comprises a plasma excited nitrogen group. The method of claim 14, wherein the second material comprises ruthenium. The method of claim 26, further comprising forming the sealing layer on the barrier layer by: - exposing the inner diameter surface of the at least all through hole through hole and the surface of the bottom wall to a dicyclopentane a first precursor of the ruthenium compound, for an exposure time sufficient to complete a self-limiting reaction of the bicyclopentanyl compound with the inner diameter surface and the bottom wall surface; - flushing the bicyclopentanyl compound from the processing chamber The inner diameter of the at least all through hole through hole and the bottom wall are exposed to a second precursor comprising a plasma-generated nitrogen group and being oxygen-free; - flushing the nitrogen groups and reaction by-products from the processing chamber; - repeating the exposure and rinsing steps as above until the sealing layer has a thickness of at least 4 Å. The method of claim 27, further comprising the step of forming the nucleation layer on the sealing layer by: - exposing the inner diameter surface of the at least all through hole through hole and the surface of the bottom wall to include one a first precursor of a dicyclopentanyl compound; - rinsing the dicyclopentanyl compound and reaction by-products from the processing chamber; - exposing the inner diameter surface of the at least all through hole through hole and the surface of the bottom wall a second precursor of un-encapsulated oxygen; - flushing the oxygen and reaction by-products from the processing chamber; - repeating the exposure and rinsing steps as described above, until the nucleation layer has a thickness of at least 49 Å until. The method of claim 28, further comprising metallizing the through via with copper, wherein the copper is applied to the nucleation layer.