Sn Compound Research Articles

Ag Electromigration Against Electron Flow in Sn5Ag/Cu Solder Bump

A phenomenon that can result in electromigration suppression in solder bumps on Cu pads is reported. Under certain current stressing conditions, Ag migrates against the electron flow and forms a Ag 3 Sn compound layer at the cathode Sn5Ag/Cu interface. This phenomenon implies that it is the electrostatic force rather than the typical wind force that is the dominant electromigration force acting on the Ag solute atoms in the Sn matrix. The Ag 3 Sn compound layer formed at the Sn5Ag/Cu joint interface could effectively retard electromigration-induced consumption on the Cu bump pad.

Solid-State Reactive Diffusion between Sn and Electroless Ni–P at 473 K

Nickel–phosphorus alloys are electrolessly deposited onto Cu-base conductors to suppress formation of Cu–Sn compounds during soldering using Sn-base solders. However, a Ni–Sn compound is produced during soldering, and continuously grows during energization heating at solid-state temperatures. To examine influence of P on the growth behavior of the Ni–Sn compound during energization heating, the kinetics of the solid-state reactive diffusion between Sn and electroless Ni–P alloys was experimentally determined at 473 K in the present study. For the experiment, pure Cu sheets were electrolessly deposited with Ni–P alloys containing 4.6 at%, 18.5 at% and 20.4 at% of P, and then sandwiched between pure Sn plates. Such Sn/(Ni–P)/Cu/(Ni–P)/Sn diffusion couples were isothermally annealed at 473 K for various periods up to 1307 h. During annealing, a layer of Ni3Sn4 is formed along the Sn/(Ni–P) interface in the diffusion couple. The annealing time dependence of the mean thickness of the Ni3Sn4 layer is expressed by a parabolic relationship. The parabolic coefficient slightly increases with increasing P concentration in the Ni–P. Thus, P in the Ni–P lightly accelerates the growth of Ni3Sn4 at the interconnection between the Ni–P and the Sn-base solder. Using the experimentally determined values of the parabolic coefficient, the interdiffusion coefficient in Ni3Sn4 was analytically evaluated by a mathematical model. The acceleration effect of P on the growth of Ni3Sn4 is quantitatively explained by the dependence of the interdiffusion coefficient on the P concentration in the Ni–P. [doi:10.2320/matertrans.MRA2008266]

Gold Embrittlement of Solder Joints in Wafer-Level Chip-Scale Package on Printed Circuit Board With Ni/Au Surface Finish

In this paper, the effect of gold amount on the gold embrittlement of solder balls in wafer-level chip-scale package (WLCSP) CSP 80 is investigated. First, precisely controlled amounts of gold were added artificially to solder balls through a reflow process. It is found that for CSP 80 without Au, after 2000 h of thermal aging at 150 degC, the solder balls still fail in the bulk solder. When Au is incorporated, brittle failure occurs after 1000 and 200 h for CSP 80 with 0.3 wt% and 0.5 wt% of Au, respectively. Detailed inspections on the microstructure reveal that, after the reflow process, fine AuSn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> intermetallic compound (IMC) particles disperse uniformly in the bulk solder. After 200 h at 150 degC, the (Cu,Ni) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">6</sub> Sn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sub> ternary compound transforms to Cu-Au-Ni-Sn quaternary compound and the IMC at the interface of solder and under bump metallization (UBM) becomes a completely continuous layer. After 1000 hours at 150 degC, two IMC layers, light gray and dark gray, forme at the interface. EDX analysis confirms that the light and dark gray IMC layers are the (Cu,Ni,Au) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">6</sub> Sn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sub> compound. However, the light gray (Cu,Ni,Au) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">6</sub> Sn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sub> compound contains a higher amount of Au and a lower amount of Ni, while the dark gray (Cu,Ni,Au) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">6</sub> Sn <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sub> IMC contains a lower amount of Au and a higher amount of Ni. After 2000 h at 150 degC, the two IMC layer structures still exist.

Synthesis and characterization of Sn 2+ oxides with the pyrochlore structure

During synthesis of S n 2 2 + M 2 X 6+ x compounds with the pyrochlore structure, some disproportionation of the Sn 2+ always occurred. This in turn led to some incorporation of Sn 4+ into the octahedral (M) sites of the pyrochlore structure. The actual amount of Sn 4+ incorporation was determined by 119Sn Mössbauer spectroscopy for two compounds. Mössbauer spectroscopy also indicated that Sn 2+ was strongly displaced from its ideal site in the pyrochlore structure. The compounds Sn 2TiNbO 6F, Sn 2Ti 0.9Ta 1.1(O,F) 7, S n 2 2 + ( S n 0.25 4 + W 1 .22 S c 0 .53 ) O 6 .96 , and S n 1.4 2 + ( S n 0.19 4 + T i 1 .06 W 0 .75 ) O 6 .15 with the pyrochlore structure are yellow to red with band gaps determined from diffuse reflectance ranging from 1.9 to 2.3 eV. The dielectric constant of Sn 2+ pyrochlores examined ranged from 31 to 149.

Effects of volume strain due to Li–Sn compound formation on electrode potential in lithium-ion batteries

Sn and Sn-based compounds have attracted great interest as candidates for anode materials in lithium-ion batteries. Despite the great deal of attention focused on the effects of the volume change of the Sn anode during the lithiation/delithiation process on the cyclic property of the batteries, its influence on the electrode potential is still not well understood. In this study, by constructing a simple Sn–Li battery system, we have investigated the effects of the volume change associated with the formation of Li–Sn compounds on the electrode potential from the viewpoint of the Gibbs free energy and associated elastic-strain energy. Our experimental results show that (i) α-Sn, which is a low-temperature phase and in thermodynamic non-equilibrium at around 298 K (our experimental temperature), is also formed together with usual β-Sn after several cycles of the lithiation and delithiation processes and (ii) when a Sn plate-shape electrode is lithiated, the experimental electrode potential underruns the value expected thermodynamically. These experimental results can be consistently explained by considering the contribution of the elastic-strain energy to the chemical free energy of formation.

First principles calculation of elastic and lattice constants of orthorhombic Cu3Sn crystal

The structure and elastic properties of a common intermetallic compound, Cu 3 Sn, at the interface of a solder and Cu metallization were investigated by the plane-wave pseudo-potential (PW-PP) method using the generalized gradient approximation (GGA). Through energy minimization, the lattice constants of the Cu 3 Sn orthorhombic crystal were calculated to within a very small range of the experimental values. Based on the structural information, the elastic constants of Cu 3 Sn crystal were determined from the first principles calculations. Using the single crystal results, the elastic constants of the polycrystalline Cu 3 Sn compound were predicted from the continuum theories. The predictions provided reasonable agreements with experimental data available.

Effects of silver doping on electromigration of eutectic SnBi solder

Abstract Effects of silver doping on electromigration behavior of the eutectic SnBi solder are investigated. Electromigration can induce the Bi migration along with the direction of electron flow in the eutectic SnBi solder, thus Bi depletes at the cathode side but accumulates at the anode side. Plate-like Ag 3 Sn compound is formed as 0.5 wt% silver is doped into the solder. The Ag 3 Sn plates behave like roadblocks which can intercept the Bi migration from the cathode side to the anode side. Consequently, a great inconsistency is found between the Bi depletion at the cathode side and the Bi accumulation at the anode side.

Synthese und Festkörperstruktur des Koordinationspolymers {Zn[Sn(CH2SMe)4]0.5Cl2}n

AbstractSynthesis and Solid State Structure of the Coordination Polymer {Zn[Sn(CH2SMe)4]0.5Cl2}nThe tin compounds Sn(CH2SMe)4 and Sn(CH2PPh2)4 are accessible from reaction of SnCl4 with LiCH2SMe and LiCH2PPh2, respectively. X‐ray quality crystals of Sn(CH2PPh2)4 (tetragonal, ) are obtained from a benzene solution at 4 °C. The lithium methanide [Li(PMDTA)CH2PPh2], which was a starting material in the synthesis of Sn(CH2PPh2)4 crystallized from a mixture of diethyl ether and pentane at −20 °C in the monoclinic space group P21/c. The coordination polymer {Zn[Sn(CH2SMe)4]0.5Cl2}n was synthesized from Sn(CH2SMe)4 and ZnCl2 in benzene. The solid state structure of this coordination polymer reveals that {Zn[Sn(CH2SMe)4]0.5Cl2}n possesses an infinite [Zn‐SMe‐CH2‐Sn‐CH2‐SMe‐]‐chain as its backbone (monoclinic P21/c).

Influence of Si on reactive diffusion between Au and Sn at solid-state temperatures

Influence of Si on the kinetics of the reactive diffusion between Au and Sn was experimentally examined at solid-state temperatures. Binary Sn–Si alloys with Si concentrations of 1 and 3 mass% were used to prepare (Sn–Si)/Au/(Sn–Si) diffusion couples by a diffusion bonding technique. The diffusion couples were isothermally annealed at temperatures of T = 433, 453 and 473 K for various times up to 200 h in an oil bath with silicone oil. After annealing, AuSn 4, AuSn 2 and AuSn layers were observed at the (Sn–Si)/Au interface in the diffusion couple. The total thickness of the Au–Sn compound layers is expressed as a power function of the annealing time. The exponent of the power function takes values between 0.37 and 0.41. The exponent smaller than 0.5 indicates that grain boundary diffusion as well as volume diffusion contributes to the rate-controlling process of the reactive diffusion and grain growth occurs at certain rates in the compound layers. The higher the Si concentration of the Sn–Si alloy is, the slower the overall growth of the compound layers occurs. This indicates that the addition of Si into the Sn-base solder alloy decelerates growth of the Au–Sn compounds at the interconnection between Au/Ni/Cu multilayer conductor and Sn-base solder alloys during energization heating.

Kinetic analysis of the interfacial reactions in Ni/Sn/Cu sandwich structures

The mutual interaction between Sn/Ni and Sn/Cu interfacial reactions in a Ni/Sn/Cu sandwich sample has been studied. The major interfacial reaction product on the Cu side was Cu6Sn5, while on the Ni side, a ternary (Cu,Ni)6Sn5 compound layer was formed. We found that the growth kinetics of the interfacial compound layers on both sides reached a steady state in the late reflow stage. The interfacial compound layer on the Cu side retained a constant thickness. On the other hand, the interfacial compound layer on the Ni side grew at a relatively fast rate, which was found to be linear with time. Our results indicate that the growth of the ternary (Cu,Ni)6Sn5 compound layer was controlled by the Cu dissolution flux at the solder/Cu6Sn5 compound interface. The dissolution constant of the Cu6Sn5 compound into the molten Sn was determined to be 0.13 μm/s.

Study of electromigration-induced Cu consumption in the flip-chip Sn∕Cu solder bumps

The Cu consumption in flip-chip Sn∕Cu solder joint structures, both with and without current stressing was studied. The Cu consumption activation energy without current stressing was determined to be 0.93eV. With current stressing, the Cu consumption activation energy decreased to 0.66eV. We believe that the enhancement of Cu consumption by current stressing is due to the electromigration (EM) Cu atoms dissolved in the Sn to electromigrate instantaneously toward the anode side, which means that the cathode’s Cu–Sn compound layer dissolves into the Sn to satisfy the Cu solubility limit. The EM-induced Cu consumption is controlled by either the dissolution of the cathode Cu–Sn compound or by EM Cu flux in Sn. The temperature defines that the controlling step of Cu consumption was found and determined to be 129°C by equating the dissolution flux in the Cu–Sn compound and the EM Cu flux in Sn. When the EM temperature is higher than the critical temperature, the Cu–Sn compound dissolution process controls the Cu consumption. In this case, a constant interfacial Cu–Sn compound thickness remains at the cathode interface, which is determined by the balance between the Cu–Sn compound dissolution and the chemical Cu flux. If the EM temperature is lower than the critical temperature, the EM Cu flux in the Sn controls the Cu consumption. The growth of Cu–Sn compound at cathode is controlled by the EM Cu flux in Sn and the chemical Cu flux.

Study of interfacial reactions in Sn–3.5Ag–3.0Bi and Sn–8.0Zn–3.0Bi sandwich structure solder joint with Ni(P)/Cu metallization on Cu substrate

In this paper, the coupling effect in Sn–3.5Ag–3.0Bi and Sn–8.0Zn–3.0Bi solder joint with sandwich structure by long time reflow soldering was studied. It was found that the interfacial compound at the Cu substrate was binary Cu–Sn compound in Sn–Ag–Bi solder joint and Cu 5Zn 8 phase in Sn–Zn–Bi solder joint. The thickness of the Cu–Zn compound layer formed at the Cu substrate was greater than or equal to that of Cu–Sn compound layer, although the reflow soldering temperature of Sn–Zn–Bi (240 °C) was lower than that of Sn–Ag–Bi (250 °C). The stable Cu–Zn compound was the absolute preferential phase in the interfacial layer between Sn–Zn–Bi and the Cu substrate. The ternary (Cu, Ni) 6Sn 5 compound was formed at the Sn–Ag–Bi/Ni(P)–Cu metallization interface, and a complex alloy Sn–Ni–Cu–Zn was formed at the Sn–Zn–Bi/Ni(P)–Cu metallization interface. It was noted that Cu atoms could diffuse from the Cu substrate through the solder matrix to the Ni(P)–Cu metallization within 1 min reflow soldering time for both solder systems, indicating that just 30 s was long enough for Cu to go through 250 μm diffusion length in the Sn–Ag–Bi solder joint at 250 °C. The coupling effect between Ni(P)/Cu metallization and Cu substrate was confirmed as the type of IMCs at Ni(P) layer had been changed from Ni–Sn system to Cu–Sn system apparently by the diffusion effect of Cu atoms. The (Cu, Ni) 6Sn 5 layer at the Ni(P)/Cu metallization grew significantly and its thickness was even greater than that of the Cu–Sn compound on the opposite side, however the growth of the complex alloy including Sn, Ni, Cu and Zn on the Ni(P)/Cu metallization was suppressed.

Current density dependence of electromigration-induced flip-chip Cu pad consumption

Current density dependence on the mechanism of the electromigration-induced flip-chip Cu pad consumption was observed. A critical current density was determined, which defines the consumption mechanism of Cu pad. Below this critical current density, a constant interfacial compound layer would be established. The mechanism whereby the Cu pad is consumed is the dissolution of the interfacial Cu–Sn compound. Above the critical current density, the interfacial compound layer continues to grow over time. The consumption of the Cu pad was then primary controlled by the total Cu flux in the interfacial Cu–Sn compound layer.

Divalent Germanium and Tin Compounds Stabilized by Sterically Bulky P∧O, PO∧O, PS∧O, and PN∧O Ligands: Synthesis and First Insights into Catalytic Application to Polyurethane Systems

A sterically bulky chelating phosphine, t Bu 2 P-CH 2 -C(CF 3 ) 2 OH (1), was shown to stabilize divalent tin and germanium compounds: M[-O-C(CF 3 ) 2 CH 2 P t Bu 2 ] 2 (6, M = Sn; 14, M = Ge). Oxidizing reagents, e.g., sulfur, pyridine-N-oxide, and 1-azidoadamantane, reacted with divalent tin 6 on the phosphorus ligands exclusively, preserving the divalent state of tin in the resultant compounds Sn[-O-C(CF 3 ) 2 -CH 2 P(S) t Bu 2 ] 2 (7), Sn[-O-C(CF 3 ) 2 CH 2 P(O) t Bu 2 ] 2 (11) and Sn[-O-C(CF 3 ) 2 CH 2 P t Bu 2 ],[-O-C(CF 3 ) 2 -CH 2 P(N 3 -Adamantyl) t Bu 2 ] 2 (12). The divalent germanium compound 14 was found to be more prone to oxidation to the tetravalent state. For example, the reaction with 1-azidoadamantane gave tetravalent germanium compounds Ge[-O-C(CF3) 2 CH 2 P(-) t Bu],[-O-C(CF 3 ) 2 CH 2 P(=N-) t Bu 2 ] (16) and [Adaman-tyl],[-O-C(CF 3 ) 2 CH 2 P(=N-)]Ge-O-Ge[-O-C(CF 3 ) 2 CH 2 P(tBu) 2 (=N-)],[Adamantyl] (17). A Ge-O-Ge bridge in 17 is very linear, with an angle Ge-O-Ge of 177.4(2)°. According to X-ray analyses the intramolecular M-P bond lengths are among the longest known for this kind of bonding: 3.228(4) A for P-Sn in 12 and 2.7585(12) A for P-Ge in 14. The divalent tin compounds 6 and 7 were found to be efficient catalysts for the formation of polyurethanes. The divalent germanium compound 14 was active in polyurethane formation, but it was an order of magnitude less active than corresponding tin analogue 6.

Inverse Perovskites (RE3N)Sn with RE = La, Ce, Pr, Nd, Sm: Preparation, Crystal Structures and Physical Properties

The ternary compounds (RE3N)Sn with RE = La, Ce, Pr, Nd, Sm were prepared starting from the elements. The compounds with RE = La, Ce, Pr were obtained as single phase materials according to X-ray powder diffraction patterns, which also indicate the cubic inverse perovskite crystal structure (space group Pm3̄m, La: a = 509.48(2) pm, Ce: a = 501.59(2) pm, Pr: a = 497.53(2) pm, Nd: a = 494.70(5) pm, Sm: a =488.35(9) pm). Chemical analyses proof the correct composition and particularly the absence of nonmetallic constituents next to nitrogen. All studied compounds show metallic characteristics in the electrical resistivity. Magnetic susceptibility measurements indicate (La3N)Sn to be a Pauli-paramagnet. Initially observed superconductivity was traced down to be due to thin La films on the surface of the grains. The Ce and Pr containing compounds show the behavior of 4f1 ions and 4f2 ions, and order antiferromagnetically at 6.8(2) K and 48(1) K, respectively.

Phase Equilibria in the Sn-Rich Corner of the Sn–Cu–Ni Ternary Alloy System at 240 °C

The interfacial reactions between solders and under bump metallization (UBM) have been of great interest recently in flip chip technology. Intermetallic compounds (IMCs), i.e., (Cu,Ni)6Sn5 and (Ni,Cu)3Sn4, usually formed between solders and UBM. To fully understand the interfacial reactions and phase transformation phenomenon, a suitable phase diagram concerning solders, IMCs, and UBM materials is required. In particular, a Sn-rich phase region in the Sn–Cu–Ni ternary diagram is very critical in determining the concentration tendency of x and y values in (Ni1−x,Cux)3Sn4 and (Cu1−y,Niy)6Sn5 compounds. In this study, ternary Sn–Cu–Ni alloys were prepared and annealed at 240 °C. Three equilibrium phases, Sn, Ni3Sn4, and Cu6Sn5, were identified by x-ray diffraction analysis and also showed in backscattered electron imaging. Using electron probe microanalysis quantitative analysis, three acme compositions of the ternary region in the Sn–Cu–Ni isotherm near the Sn-rich corner were determined as 98.5 at.% Sn, (Ni0.80, Cu0.20)3Sn4 and (Cu0.59,Ni0.41)6Sn5. In addition, the solubility of Cu and Ni in (Ni,Cu)3Sn4 and (Cu,Ni)6Sn5 compounds was evaluated. Finally, the isothermal section of the ternary Sn–Cu–Ni system at 240 °C was proposed on the basis of experimental results in this study.

Novel Compounds Sn20Zn4P22‐νI8 (ν = 1.2), Sn17Zn7P22I8, and Sn17Zn7P22Br8: Synthesis, Properties, and Special Features of Their Clathrate‐Like Crystal Structures.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Reactive diffusion between Pd and Sn at solid-state temperatures

The kinetics of the reactive diffusion between Pd and Sn at solid-state temperatures was experimentally examined using Sn/Pd/Sn diffusion couples prepared by a diffusion bonding technique. The diffusion couples were isothermally annealed at temperatures of T = 433, 453 and 473 K for various times up to 300 h in an oil bath with silicone oil. After annealing, PdSn 4, PdSn 3 and PdSn 2 compound layers were observed at T = 433 K, but only PdSn 4 and PdSn 3 layers were recognized at T = 453 and 473 K. The total thickness l of the Pd–Sn compound layers is mathematically described as a power function of the annealing time t as follows: l = k( t/ t 0) n , where t 0 is unit time, 1 s. The diameter d of the columnar grain in the compound layers is also expressed as a power function of the annealing time t: d = k d( t/ t 0) p . At T = 433–473 K, n is close to 0.5, and p takes values of 0.14–0.17. Such values of p indicate that the grain growth occurs at certain rates in the compound layers. Nevertheless, the total thickness l is almost proportional to the square root of the annealing time t. Thus, it is concluded that the volume diffusion is the rate-controlling process of the reactive diffusion between Pd and Sn.

Effects of Cu Contents in Sn–Cu Solder on the Composition and Morphology of Intermetallic Compounds at a Solder/Ni Interface

The reaction between Sn–xCu (x = 0.1, 0.3, 0.7, 0.9, and 1.5 wt%) solder alloys and Ni at 260, 280, and 290 °C for 60 s was studied to reveal the effect of Cu content on the composition and morphology of intermetallic compounds (IMCs) formed at the interface between solder and substrate. The results indicated that Cu concentration greatly affects both the composition and morphology of the IMC between the solder and Ni substrate. In particular, when the Cu concentration was less than or equal to0.3 wt%, (CuxNi1−x)3Sn4 IMCs were formed at the interface. When the Cu concentration was 0.7 wt%, large facets type of (CuxNi1−x)6Sn5 were mixed with (CuxNi1−x)3Sn4 in the IMC layer. At Cu concentrations higher than the eutectic one, e.g., 0.9 and 1.5 wt%, stick-shaped (CuxNi1−x)6Sn5 compounds were detected, but the (CuxNi1−x)3Sn4 IMCs disappeared. The formation and growth mechanism of the (CuxNi1−x)6Sn5 compound were analyzed. The evolution tendency of the composition and morphology of the IMCs at the three testing temperatures was found to be the same.

Novel compounds Sn 20Zn 4P 22− vI 8 ( [formula omitted]), Sn 17Zn 7P 22I 8, and Sn 17Zn 7P 22Br 8: Synthesis, properties, and special features of their clathrate-like crystal structures

Tin–zinc pnictidehalides Sn 20Zn 4P 22− v I 8 ( v = 1.2 ), Sn 17Zn 7P 22I 8, and Sn 17Zn 7P 22Br 8 have been prepared as single-phase samples by a standard ampoule procedure. The compounds are isotypic and possess the structure of type-I gas hydrate (clathrate-I type). They all crystallize in the cubic space group Pm 3 ¯ n (no. 223) with the unit cell parameters a = 10.883 ( 2 ) Å (Sn 20Zn 4P 22− v I 8), a = 10.8458 ( 3 ) Å (Sn 17Zn 7P 22I 8), a = 10.7449 ( 2 ) Å (Sn 17Zn 7P 22Br 8), and Z = 1 . The crystal structures of all compounds have been solved from single-crystal X-ray diffraction data sets and refined to R = 0.032 (Sn 20Zn 4P 22− v I 8), R = 0.027 (Sn 17Zn 7P 22I 8), and R = 0.020 (Sn 17Zn 7P 22Br 8). In all structures tin, zinc, and phosphorus atoms form the clathrate-I framework while the guest halogen atoms are encapsulated in the cavities of the framework. The compositions of the synthesized compounds are in agreement with those predicted by using the Zintl–Klemm concept. Sn 20Zn 4P 22− v I 8 contains two partially filled metal sites and vacancies in one of the phosphorus sites and can be formulated as Sn 20Zn 4P 20.8□ 1.2I 8 (or Sn 20Zn 4P 22−1.2I 8). Sn 17Zn 7P 22I 8 and Sn 17Zn 7P 22Br 8 are vacancy-free and reveal three partially filled positions of metal atoms. Thus, Sn 17Zn 7P 22 X 8 and Sn 20Zn 4P 20.8□ 1.2I 8, being the limiting and the intermediate compositions, respectively, of the solid solutions of a general formula Sn 24− n Zn n P 22− v X 8 ( v = ( 14 − 2 n ) / 5 , X=Br, I), show different mechanisms of the structural stabilization. The 119Sn Mössbauer together with the 31P and 119Sn NMR spectra confirm the local environment of tin and phosphorus atoms in the structures of Sn 17Zn 7P 22I 8 and Sn 17Zn 7P 22Br 8. The compounds Sn 17Zn 7P 22I 8 and Sn 17Zn 7P 22Br 8 display diamagnetic and semiconducting behavior. The heat capacity has been measured for Sn 17Zn 7P 22I 8 in a temperature range of 6 K to 400 K. No low-temperature phase transitions have been detected in the measurements.